WO2019040442A1

WO2019040442A1 - Soap compositions and treatment methods for the mitigation of winter season related pruritus

Info

Publication number: WO2019040442A1
Application number: PCT/US2018/047236
Authority: WO
Inventors: Toshio Horikoshi; Brian D. FIGURA; Krishnan Chari; Shui-Jen Raymond Hsu; Dongcui LI; Sinan Li; Robert Jacobs; Yi Yang; Qunhua XU
Original assignee: Lubrizol Advanced Materials, Inc.
Priority date: 2017-08-22
Filing date: 2018-08-21
Publication date: 2019-02-28
Also published as: JP2020531533A

Abstract

The disclosed technology relates to a method for the treatment of a pruritic skin condition caused by exposure to a low humidity environment comprising applying to the scalp and/or skin a composition comprising: a) at least one salt of a fatty acid; b) a crosslinked nonionic amphiphilic emulsion polymer; c) water; and d) an optional surfactant different than a).

Description

SOAP COMPOSITIONS AND TREATMENT METHODS FOR THE MITIGATION OF WINTER SEASON RELATED PRURITUS

TECHNOLOGICAL FIELD

[0001] The present technology relates to a method for mitigating pruritus caused by prolonged exposure to low humidity conditions comprising applying to the scalp and skin of a mammalian subject a cleansing composition including at least one fatty acid soap and least one crosslinked nonionic amphiphilic polymer.

BACKGROUND

[0002] Many people suffer from different skin conditions that result in dryness, discoloration, edema, pain and general irritation. Some of these conditions are elicited by topical cleansing products including shampoos, body cleansers and other personal care products that contain harsh detersive surfactants. These detersive surfactants remove some of the skin's protective lipids and/or secretions which may increase the permeability and sensitivity of the skin to topically applied chemicals which would not otherwise produce irritation. A typical symptom of irritation includes itching (pruritus). Itch can be defined as a sensation which provokes the desire to scratch the area from which the sensation originates. No matter what the ultimate cause of the itch, the sensation experienced is the same and provokes the desire to scratch in order to curtail the sensation.

[0003] Environmental influences may also adversely affect the skin's barrier function and provoke irritation. Irritation results from, or is aggravated by, extremes in humidity, exposure to sunlight, and abrasive clothing. A very common condition caused by low humidity environments is known as "winter itch" in which the very low humidity conditions of winter month cold climates (particularly when accompanied by indoor heating) or long exposure to refrigerated air from air conditioners in summer month warm climates produces itchy scalp and/or skin. When cold, dry air is artificially heated it becomes even dryer, acts almost like a sponge, and "pulls" water from the skin through enhanced surface evaporation. Since water is the main "softener" of the skin, dry skin may become rough, scaly, and eventually red, inflamed, and itchy. In severe cases these changes will have the appearance of dermatitis. A treatment for "winter itch" is to: 1 ) increase the relative humidity of the air; 2) decrease the factors that may exacerbate the problem, such as excessive bathing and the use of cleansers containing harsh detersive surfactants; and 3) moisturize the skin with humectant and/or emollient containing creams, lotions, or ointments.

[0004] Efforts have been made to reduce the use of body cleansers that contain harsh synthetic surfactants by substituting the surfactant with liquid soaps derived from fatty acid salts. Liquid fatty acid soap compositions are known in the art. These soaps have been widely employed for many years as effective mild general all-purpose body cleansers. Fatty acid soaps are formulated with a myriad of different ingredients to obtain the desired cleansing effect and the requisite physical property parameters so that they can be easily stored and dispensed in a convenient manner. Fatty acid soaps must have the appropriate rheology characteristics to be flowable when dispensed from the product container but of a sufficient viscosity not run off of the skin when applied to the body. In addition, today's consumer is increasingly looking for additional benefits beyond the basic cleansing effects brought about by the traditional soap product. Efforts are continually being made to make improvements in product function and aesthetics by incorporating various adjuncts into the formulation such as moisturizers, emollients, colorants, opacifiers, perfumes, antioxidants, antibacterial agents, and the like to name a few. It has also been increasingly popular to incorporate water insoluble moieties such as microcapsules, beads, and pearlescent agents into the soap composition for delivery of actives to the skin and for product aesthetics.

[0005] In order to achieve the desired rheology profiles and to disperse the multitude of different ingredients within the soap composition, synthetic rheology modifying polymers and synthetic surfactants have been employed in an attempt to obtain a composition which is stable with respect to viscosity and visual phase homogeneity over a period of time and a wide range of temperatures. These parameters are particularly significant for liquid compositions wherein the large quantity of water in the formulation makes the establishment of a stable composition more difficult, particularly when substantially water insoluble adjuncts are dispersed in the formulation.

[0006] U.S. Patent Application Pub. No. U.S. 2007/0213243 discloses a stable soap composition comprising: (a) a crosslinked acrylic copolymer (INCI name: Acrylates Copolymer); (b) a fatty acid soap; (c) an alkalizing agent; (d) an optional surfactant; (e) an optional humectant; (f) an optional emollient; and (g) water. The composition is stabilized with the acrylic copolymer and subsequently back-acid treated with the acidifying agent to obtain compositions that are storage and phase stable over a wide temperature range.

[0007] International Pub. No. WO 2015/038601 discloses a method for mitigating pruritus caused by prolonged exposure to low humidity conditions by bathing with a liquid soap composition thickened with the crosslinked acrylic copolymer (INCI name: Acrylates Copolymer) disclosed in U.S. 2007/0213243.

[0008] The Acrylates Copolymer disclosed in U.S. 2007/0213243 and WO 2015/038601 is prepared from (meth)acrylic acid, a Ci to Cs alkyl ester of (meth)acrylic acid and a polyunsaturated crosslinker. The disclosed thickener requires neutralization with an alkalizing agent and optional back-acidification with an acidifying agent in order to build viscosity. Accordingly, the disclosed thickening agents are pH dependent meaning that the thickening mechanism relies on changing the pH of the composition in which they are contained to build viscosity.

[0009] International Pub. No. WO 2014/099573 discloses conventionally crosslinked nonionic amphiphilic polymers and their use as ocular and/or dermal irritation mitigants in surfactant containing compositions. The polymers mitigate irritation of the skin and eyes caused by harsh synthetic detersive surfactants contained in personal care cleansing compositions. The disclosed amphiphilic polymers provide tailored yield stress properties (the ability to stably suspend insoluble materials) to cleansing formulations across a wide pH range. The disclosed polymers do not require neutralization with a base or an acid in order to activate the thickening mechanism. In other words, the thickening mechanism is independent of pH. [0010] International Pub. No. WO 2015/095286 discloses a nonionic amphiphilic polymer rheology modifier crosslinked with amphiphilic crosslinking agent or a mixture of an amphiphilic crosslinking agent and a conventional crosslinking agent. The disclosed amphiphilic polymers provide tailored yield stress properties to surfactant containing cleansing formulations across a wide pH range.

[0011] While International Pub. Nos. WO 2014/099573 and WO 2015/095286 disclose fatty acid salt soaps among a myriad of anionic surfactants useful in the disclosed surfactant containing compositions, there is no recognition that pruritus caused by winter itch irritation can be treated or mitigated by a detersive combination of fatty acid soap(s), a crosslinked nonionic amphiphilic polymer, and an optional synthetic surfactant(s).

[0012] Surprisingly, we have found that liquid cleansers formulated with a fatty acid salt soap and a crosslinked nonionic amphiphilic polymer mitigate the itching effects caused by low environmental humidity that is particularly prevalent in the winter months of cold climate regions of the world.

SUMMARY OF THE TECHNOLOGY

[0013] In accordance with a general embodiment of the present technology, a liquid soap composition comprising a fatty acid salt soap base selected from at least one fatty acid salt, a crosslinked nonionic amphiphilic emulsion polymer and water utilized during normal bathing intervals to cleanse the scalp and skin mitigates the occurrence of winter itch caused by low environmental humidity.

[0014] In accordance with another general embodiment of the present technology, the cleansing soap comprises a soap base selected from at least one fatty acid salt, a crosslinked nonionic amphiphilic emulsion polymer, water and a synthetic surfactant selected from an anionic surfactant, an amphoteric surfactant, and mixtures thereof.

[0015] In accordance with still another general embodiment of the technology there is provided a method for the treatment or mitigation of a pruritic skin condition comprising applying to the scalp and/or skin at least one composition comprising: a) a soap comprising at least one fatty acid salt;

b) a crosslinked nonionic amphiphilic emulsion polymer prepared from:

i. from about 35% to about 55% by weight of at least one Ci to C5 hydroxyalkyl ester of (meth)acrylic acid;

ii. from about 10% to about 50% by weight of at least one Ci to C5 alkyl ester of (meth)acrylic acid; and

iii. from about 0.1 % to about 20% by weight of at least one associative monomer and/or a semi-hydrophobic monomer (wherein all monomer weight percentages are based on the weight of the total monounsaturated monomers);

vi. from about 0.01 to about 5 parts by weight of at least one polyunsaturated crosslinker monomer (based on 100 parts by wt. of the monounsaturated monomers utilized to prepare the polymer);

c) water; and

d) optionally at least one surfactant.

[0016] In accordance with still another embodiment of the technology there is provided a method for the treatment or mitigation of a pruritic skin condition caused by prolonged exposure to low relative humidity conditions comprising applying to the scalp and/or skin at least one composition comprising:

a) a soap comprising at least one fatty acid salt

b) a crosslinked nonionic amphiphilic emulsion polymer prepared from i. from about 40% to about 50%, or from about 42% to about 48%, or from about 44 to 46 by weight of 2-hydroxyethyl methacrylate;

ii. from about 10% to about 40%, or from about 12% to about 35%, or from about 15% to about 25% by weight of ethyl acrylate;

iii. from about 10% to about 35%, or from about 12% to about 30%, or from about 15% to about 25% by weight of butyl acrylate;

iv. from about 0.5% to about 18%, or about 1 %, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10% to about 15% by weight of an associative monomer selected from behenyl ethoxylated methacrylate (based on 100 parts by wt. of the monounsaturated monomers utilized to prepare the polymer); and v. from about 0.1 , 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9 to about 1 , or about 1 .5, 2 or 3 to about 5 parts by wt. of at least one polyunsaturated crosslinker monomer selected from an polyunsaturated amphiphilic crosslinking monomer (based on 100 parts by wt. of the monounsaturated monomers utilized to prepare the polymer);

c) water; and

d) optionally at least one surfactant.

[0017] In accordance with still another embodiment of the technology there is provided a method for the treatment or mitigation of a pruritic skin condition caused by prolonged exposure to low relative humidity conditions comprising applying to the scalp and/or skin at least one composition comprising:

a) a soap comprising at least one fatty acid salt

b) a crosslinked nonionic amphiphilic emulsion polymer prepared from i. about 44% by weight of 2-hydroxyethyl methacrylate;

ii. about 35% by weight of ethyl acrylate;

iii. about 15% by weight of butyl acrylate;

iv. about 6% by weight of behenyl ethoxylated methacrylate (based on 100 parts by wt. of the monounsaturated monomers utilized to prepare the polymer); and

v. from about 0.5 to about 2 parts by wt. of at least one polyunsaturated amphiphilic crosslinker monomer (based on 100 parts by wt. of the monounsaturated monomers utilized to prepare the polymer);

c) water; and

d) optionally at least one surfactant.

[0018] In accordance with still another embodiment of the technology there is provided a method for the treatment or mitigation of a pruritic skin condition caused by prolonged exposure to low relative humidity conditions comprising applying to the scalp and/or skin at least one composition comprising:

a) a soap comprising at least one fatty acid salt

b) a crosslinked nonionic amphiphilic emulsion polymer prepared from i. about 45% by weight of 2-hydroxyethyl methacrylate;

ii. about 15% by weight of ethyl acrylate; iii. about 25% by weight of butyl acrylate;

iv. about 15% by weight of behenyl ethoxylated methacrylate (based on 100 parts by wt. of the monounsaturated monomers utilized to prepare the polymer); and

v. from about 0.5 to about 2 parts by wt. of at least one polyunsaturated amphiphilic crosslinker monomer (based on 100 parts by wt. of the monounsaturated monomers utilized to prepare the polymer); c) water; and

d) optionally at least one surfactant.

[0019] In accordance with still another embodiment of the technology there is provided a method for the treatment or mitigation of a pruritic skin condition caused by prolonged exposure to low relative humidity conditions comprising applying to the scalp and/or skin at least one composition comprising:

a) a soap comprising at least one fatty acid salt

ii. about 20.5% by weight of ethyl acrylate;

iii. about 27.5% by weight of butyl acrylate;

iv. about 7% by weight of behenyl ethoxylated methacrylate (based on 100 parts by wt. of the monounsaturated monomers utilized to prepare the polymer); and

v. from about 0.1 to about 1 part by wt. of at least one polyunsaturated amphiphilic crosslinker monomer (based on 100 parts by wt. of the monounsaturated monomers utilized to prepare the polymer); c) water; and

d) optionally at least one surfactant. DESCRIPTION OF EXEMPLARY EMBODIMENTS

[0020] Certain embodiments of the technology disclosed herein are based on the surprising discovery that a cleansing composition comprising at least one fatty acid salt soap, a crosslinked nonionic amphiphilic emulsion polymer, water, and optionally, at least one surfactant can mitigate pruritus of the scalp and skin. [0021] In particular, it has been discovered that the soap-based cleansing composition disclosed herein can be employed during normal bathing intervals as an effective treatment for mitigating pruritus of the scalp and skin caused by prolonged exposure to low humidity environments.

[0022] As used here and throughout the present specification the term "pruritus" or "pruritic" means is a sensation that causes the desire or reflex to scratch.

[0023] As used here and throughout the present specification the term "low relative humidity" (RH) means a RH value of 50% or less in one aspect, 45% or less in another aspect, 40% or less in still another aspect, 35% or less in a further aspect, 30% or less in a still further aspect, and 25%, 20%, 15%, 10%, 5% and 1 % in an additional aspect.

[0024] By "relative humidity" is meant the ratio of the actual amount of water vapor present in a volume of air (by vapor density or vapor pressure) at a given temperature to the maximum amount of water vapor that could exist in the air at that temperature (by saturation vapor density or saturation vapor pressure), expressed as a percentage, and can be calculated by the equations:

RH = (actual vapor density)/(saturation vapor density) x 100

or

RH = (actual vapor pressure)/(saturation vapor pressure) x 100

[0025] By "prolonged exposure to low relative humidity" means exposure to low humidity conditions for a sufficient time to develop pruritus.

[0026] As used here and throughout the specification "winter itch" is a pruritic condition caused by exposure to cold winter air and/or to low humidity conditions.

[0027] By "cold winter air" is meant a temperature of 20°C or less in one aspect, 15°C or less in another aspect, 10°C or less in still another aspect, and 9°C, 8°C, 7°C, 6°C, 5°C, 4°C, 3°C, 2°C, 1 °C, 0°C, -5°C, -10°C and -15°C or less in a further aspect. [0028] As used herein, the prefix "(meth)acryl" includes "acryl" as well as "methacryl". For example, the term "(meth)acrylic acid" includes both acrylic acid and methacrylic acid.

[0029] The term "nonionic" as used herein encompasses both a monomer, monomer composition or a polymer polymerized from a monomer composition devoid of ionic or ionizable moieties ("nonionizable"), and a "substantially nonionic" monomer, monomer composition or polymer polymerized from a monomer composition.

[0030] An ionizable moiety is any group that can be made ionic by neutralization with an acid or a base

[0031] An ionic or an ionized moiety is any moiety that has been neutralized by an acid or a base.

[0032] By "substantially nonionic" is meant that the monomer, monomer composition or polymer polymerized from a monomer composition contains less than or equal to 15 wt.% in one aspect, less than or equal to 10 wt.% in another aspect, less than or equal to 5 wt. % in still another aspect, less than or equal to 3 wt.% in a further aspect, less than or equal to 1 wt.% in a still further aspect, less than or equal to 0.5 wt.% in an additional aspect, less than or equal to 0.1 wt.% in a still additional aspect, and less than or equal to 0.05 wt.% in a further aspect, of an ionizable and/or an ionized moiety. Those of ordinary skill in the art will recognize that depending on the commercial source, some nonionic monomers may contain residual amounts of a monomer with ionic or ionizable character. The amount of residual monomer in a nonionic monomer composition that contains ionic or ionizable moieties can range from 0, 0.05, 0.5, 1 , 2, 3, 4, or 5 to 15 wt.% based on the weight of the particular nonionic monomer.

[0033] The phrase "at least one" means one or more of a particular component and thus includes individual components as well as mixtures/combinations of individually recited components.

[0034] The methods, polymers, components, and compositions of the present technology may suitably comprise, consist of, or consist essentially of the components, elements, steps, and process delineations described herein. The technology illustratively disclosed herein suitably may be practiced in the absence of any element, component or step which is not specifically disclosed herein.

[0035] Unless otherwise stated, all percentages, parts, and ratios expressed herein are based upon the total composition weight of the soap cleansing composition.

[0036] When referring to a specified monomer(s) that is incorporated into a polymer of the disclosed technology, it will be recognized that the monomer(s) will be incorporated into the polymer as a unit(s) derived from the specified monomer(s) (e.g., repeating unit).

[0037] The term "personal care" as used herein includes, without being limited thereto, cosmetics, toiletries, cosmeceuticals, beauty aids, insect repellents, personal hygiene and cleansing products applied to the body, including the skin, hair, scalp, and nails of humans and animals.

[0038] Here, as well as elsewhere in the specification and claims, individual numerical values (including carbon atom numerical values), or limits, can be combined to form additional non-disclosed and/or non-stated ranges.

[0039] The headings provided herein serve to illustrate, but not to limit the disclosed technology in any way or manner.

[0040] In addition to the foregoing ingredients, the cleansing compositions can include other optional adjuncts conventionally used in soaps. These include, for example, one or more emollients, one or more humectants, one or more preservatives, one or more viscosity adjusting agents, one or more skin conditioning agents, one or more hair conditioning agents, one or more antibacterial agents, one or more antioxidants, one or more fragrances, one or more colorants, one or more chelating (sequestering) agents and one or more insoluble materials. These optional materials are described in more detail below.

[0041] The selection and the amounts of the forgoing ingredients will be dependent upon the desired liquid soap end product of the invention. For example, a hand soap, body wash, shampoo, and facial cleanser can contain different ingredients as well as varying amounts of the same ingredient. The choice and amount of ingredients in formulated compositions of the invention will vary depending on the product and its function, as is well known to those skilled in the formulation arts.

[0042] While overlapping weight ranges for the various ingredients that make up the cleansing soap composition will be expressed for various embodiments of the disclosed technology, it should be readily apparent that the specific amount of each component in the composition will be selected from its disclosed range such that the desired amount of each component will be adjusted so that the sum of all components in the liquid soap composition totals 100 wt. %.

Fatty Acid Salt Soap

[0043] In one aspect of the disclosed technology the soap composition contains at least one the fatty acid salt soap containing from about 8 to about 22 carbon atoms. In another aspect of the disclosed technology the soap composition contains at least one fatty acid salt soap containing from about 10 to about 18 carbon atoms. In a further aspect of the disclosed technology the soap composition contains at least one fatty acid salt soap containing from about 12 to about 16 carbon atoms. The fatty acids utilized in the soaps can be saturated and unsaturated and can be derived from synthetic sources, as well as from the hydrolysis of fats and natural oils. Exemplary saturated fatty acids include but are not limited to octanoic, decanoic, lauric, myristic, pentadecanoic, palmitic, margaric, steric, isostearic, nonadecanoic, arachidic, behenic, and the like, and mixtures thereof. Exemplary unsaturated fatty acids include but are not limited to myristoleic, palmitoleic, oleic, linoleic, linolenic, and the like, and mixtures thereof. The fatty acids can be derived from animal fat such as tallow, lard, poultry fat or from vegetable sources such as coconut oil, red oil, palm kernel oil, palm oil, cottonseed oil, linseed oil, sunflower seed oil, olive oil, soybean oil, peanut oil, corn oil, safflower oil, sesame oil, rapeseed oil, canola oil, and mixtures thereof.

[0044] The soap can be prepared by a variety of well known means such as by the direct base neutralization of a fatty acid or mixtures thereof or by the saponification of suitable fats and vegetable oils or mixtures thereof with a suitable base. Exemplary bases include potassium hydroxide, potassium carbonate, sodium hydroxide and alkanol amines such as triethanolamine. Generally, the fat or oil is heated until liquefied and a solution of the desired base is added thereto. Soaps included in a personal care composition utilized in the method of the disclosed technology can be made, for example, by a classic kettle process or modern continuous manufacturing process wherein natural fats and oils such as tallow or coconut oil or their equivalents are saponified with an alkali metal hydroxide using procedures well known to those skilled in the art. Alternatively, soaps can be made by the direct neutralization of free fatty acids such as lauric acid (C12), myristic acid (CM), palmitic acid (C16), steric acid (Cie), isostearic (Cie), and mixtures thereof, with an alkali metal hydroxide or carbonate.

[0045] The amount of the at least one fatty acid salt soap that is employed in the soap composition of the present technology ranges from about 10% to about 35% by wt. in one aspect, from about 12% to about 30% by wt. in another aspect, from about 15% to about 25% by wt. in still another aspect, and from about 18% to about 20% by wt. , based on the total weight of the composition.

[0046] In one aspect of the disclosed technology, the fatty acid salt soap comprises a fatty acid salt wherein the fatty acid is selected from a mixture of lauric acid, myristic acid, and steric acid. In another aspect, the fatty acid salt soap comprises a fatty acid salt wherein the fatty acid is selected from a mixture of lauric acid, myristic acid, and isostearic acid. In still another aspect, the fatty acid salt soap comprises a fatty acid salt wherein the fatty acid is selected from a mixture of lauric acid, myristic acid, and palmitic acid. In a further aspect, the fatty acid salt soap comprises a fatty acid salt wherein the fatty acid is selected from a mixture of lauric acid, myristic acid, palmitic acid, and steric acid, an alkali metal fatty acid salt soap. In another aspect of the technology, the fatty acid soap is the potassium salt of a fatty acid.

Amphiphilic Polymer

[0047] In one aspect of the disclosed technology, the crosslinked nonionic, amphiphilic polymer is polymerized from monomer components that contain free radically polymerizable monounsaturation. In one embodiment, the crosslinked nonionic amphiphilic polymer useful in the practice of the disclosed technology are prepared from a monomer mixture comprising: a) at least one monomer selected from a Ci to Cs hydroxyalkyl (meth)acrylate; b) at least one monomer selected from a Ci to Cs alkyl (meth)acrylate; c) at least one monomer selected from an associative monomer, a semi-hydrophobic monomer and mixtures thereof; and d) at least one polyunsaturated crosslinking monomer.

[0048] In one embodiment, the crosslinked nonionic amphiphilic polymer useful in the practice of the disclosed technology is prepared from a monomer mixture comprising: a) at least one monomer selected from 2-hydroxyethyl methacrylate; b) at least one monomer selected from a ethyl acrylate, butyl acrylate, and mixtures thereof; c) at least one monomer selected from an associative monomer; and mixtures thereof; d) an amphiphilic crosslinking monomer; and e) an amphiphilic additive, wherein said polymerizable monomer mixture containing the amphiphilic additive is free of a protective colloid and/or a polymeric stabilizer. In one embodiment, the monomer mixture is polymerized in a medium containing a protective colloid, a polymeric steric stabilizer and combinations thereof.

[0049] The hydroxy(Ci-Cs)alkyl (meth)acrylates can be structurally represented by the following formula:

wherein R¹ is hydrogen or methyl and R² is an divalent alkylene moiety containing 1 to 5 carbon atoms, wherein the alkylene moiety optionally can be substituted by one or more methyl groups. Representative monomers include 2- hydroxyethyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, 4- hydroxybutyl(meth)acrylate, and mixtures thereof.

[0050] In one aspect, 35% to about 55%, or from about 40% to about 50% or from about 42% to about 48%, or from about 44% to about 46% by weight of the at least one Ci to Cs hydroxyalkyl ester of (meth)acrylic (based on the total weight of the monounsaturated monomers in the polymerization medium) is utilized to prepare the polymer.

[0051] The (C1 -C5) alkyl (meth)acrylates can be structurally represented by the following formula:

wherein R¹ is hydrogen or methyl and R³ is Ci to Cs alkyl. Representative monomers include but are not limited to methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, sec-butyl (meth)acrylate, and iso-butyl (meth)acrylate, and mixtures thereof.

[0052] In one aspect, from about 10% to about 50%, or from about 12% to about 45%, or from about 15% to about 40%, or from about 20% to about 35 %, or from about 25% to about 30% by weight of the at least one Ci to Cs alkyl ester of (meth)acrylic acid (based on the total weight of the monounsaturated monomers in the polymerization medium) is utilized to prepare the polymer.

[0053] The associative monomer of the disclosed technology has an ethylenically unsaturated end group portion (i) for addition polymerization with the other monomers of the disclosed technology; a polyoxyalkylene mid-section portion (ii) for imparting selective hydrophilic and/or hydrophobic properties to the product polymer, and a hydrophobic end group portion (iii) for providing selective hydrophobic properties to the polymer.

[0054] The portion (i) supplying the ethylenically unsaturated end group can be a residue derived from an α,β-ethylenically unsaturated monocarboxylic acid. Alternatively, portion (i) of the associative monomer can be a residue derived from an allyl ether or vinyl ether; a nonionic vinyl-substituted urethane monomer, such as disclosed in U.S. Reissue Patent No. 33,156 or U.S. Patent No. 5,294,692; or a vinyl-substituted urea reaction product, such as disclosed in U.S. Patent No. 5,01 1 ,978; the relevant disclosures of each are incorporated herein by reference.

[0055] The mid-section portion (ii) is a polyoxyalkylene segment of about 2 to about 150 in one aspect, from about 10 to about 120 in another aspect, and from about 15 to about 60 in a further aspect of repeating C2 -C4 alkylene oxide units. The mid-section portion (ii) includes polyoxyethylene, polyoxypropylene, and polyoxybutylene segments, and combinations thereof comprising from about 2 to about 150 in one aspect, from about 5 to about 120 in another aspect, and from about 10 to about 60 in a further aspect of ethylene, propylene and/or butylene oxide units, arranged in random or block sequences of ethylene oxide, propylene oxide and/or butylene oxide units.

[0056] The hydrophobic end group portion (iii) of the associative monomer is a hydrocarbon moiety belonging to one of the following hydrocarbon classes: a C8-C30 linear alkyl, a C8-C30 branched alkyl, a C8-C30 carbocyclic alkyl, a C2-C30 alkyl-substituted phenyl, an araalkyl substituted phenyl, and aryl-substituted C2-C30 alkyl groups.

[0057] Non-limiting examples of suitable hydrophobic end group portions (iii) of the associative monomers are linear or branched alkyl groups having about 8 to about 30 carbon atoms, such as capryl (Ce), iso-octyl (branched Ce), decyl (C10), lauryl (C12), myristyl (CM), cetyl (C16), cetearyl (C16-C18), stearyl (Cie), isostearyl (branched Cie), arachidyl (C20), behenyl (C22), lignoceryl (C24), cerotyl (C26), montanyl (C28), melissyl (C30), and the like.

[0058] Examples of linear and branched alkyl groups having about 8 to about 30 carbon atoms that are derived from a natural source include, without being limited thereto, alkyl groups derived from hydrogenated peanut oil, soybean oil and canola oil (all predominately Cie), hydrogenated tallow oil (C16-C18), and the like; and hydrogenated C10-C30 terpenols, such as hydrogenated geraniol (branched C10), hydrogenated farnesol (branched C15), hydrogenated phytol (branched C20), and the like.

[0059] Non-limiting examples of suitable C2-C30 alkyl-substituted phenyl groups include octylphenyl, nonylphenyl, decylphenyl, dodecylphenyl, hexadecylphenyl, octadecylphenyl, isooctylphenyl, sec-butylphenyl, and the like. [0060] Exemplary aryl-substituted C2-C40 alkyl groups include, without limitation thereto, styryl (e.g., 2-phenylethyl), distyryl (e.g., 2,4-diphenylbutyl), tristyryl (e.g., 2,4,6-triphenylhexyl), 4-phenylbutyl, 2-methyl-2-phenylethyl, tnstyrylphenolyl, and the like.

[0061] Suitable C8-C30 carbocylic alkyl groups include, without being limited thereto, groups derived from sterols from animal sources, such as cholesterol, lanosterol, 7-dehydrocholesterol, and the like; from vegetable sources, such as phytosterol, stigmasterol, campesterol, and the like; and from yeast sources, such as ergosterol, mycosterol, and the like. Other carbocyclic alkyl hydrophobic end groups useful in the disclosed technology include, without being limited thereto, cyclooctyl, cyclododecyl, adamantyl, decahydronaphthyl, and groups derived from natural carbocyclic materials, such as pinene, hydrogenated retinol, camphor, isobornyl alcohol, and the like.

[0062] Useful associative monomers can be prepared by any method known in the art. See, for example, U.S. Patents No. 4,421 ,902 to Chang et al.; No. 4,384,096 to Sonnabend; No. 4,514,552 to Shay et al.; No. 4,600,761 to Ruffner et al.; No. 4,616,074 to Ruffner; No. 5,294,692 to Barron et al.; No. 5,292,843 to Jenkins et al.; No. 5,770,760 to Robinson; and No. 5,412, 142 to Wilkerson, III et al.; the pertinent disclosures of which are incorporated herein by reference.

[0063] In one aspect, exemplary associative monomers include those represented by formulas below:

wherein R¹ is hydrogen or methyl; A is -CH₂C(0)0- -C(0)0- -0-, -CH2O- -NHC(0)NH- -C(0)NH- -Ar-(CE₂)z-NHC(0)0- -Ar-(CE₂)z-NHC(0)NH- or -CH2CH2NHC(0)-; Ar is a divalent arylene (e.g., phenylene); E is H or methyl; z is 0 or 1 ; k is an integer ranging from about 0 to about 30, and m is 0 or 1 , with the proviso that when k is 0, m is 0, and when k is in the range of 1 to about 30, m is 1 ; D represents a vinyl or an allyl moiety; (R¹⁵-0)n is a polyoxyalkylene moiety, which can be a homopolymer, a random copolymer, or a block copolymer of C2-C4 oxyalkylene units, R¹⁵ is a divalent alkylene moiety selected from C2H4, C3H6, or C4H8, and combinations thereof; and n is an integer in the range of about 2 to about 150 in one aspect, from about 10 to about 120 in another aspect, and from about 15 to about 60 in a further aspect; Y is -R¹⁵0- -R¹⁵NH- -C(O)-, -C(0)NH- -R¹⁵NHC(0)NH- or -C(0)NHC(0)-; R¹⁶ is a substituted or unsubstituted alkyl selected from a C8-C30 linear alkyl, a C8-C30 branched alkyl, a C8-C30 carbocyclic alkyl, a C2-C30 alkyl-substituted phenyl, an araalkyl substituted phenyl, and an aryl-substituted C2-C30 alkyl; wherein the R¹⁶ alkyl group, aryl group, phenyl group optionally comprises one or more substituents selected from the group consisting of a hydroxyl group, an alkoxyl group, benzyl group phenylethyl group, and a halogen group.

[0064] In one aspect, the hydrophobically modified associative monomer is an alkoxylated (meth)acrylate having a hydrophobic group containing 8 to 30 carbon atoms represented by the following formula:

wherein R¹ is hydrogen or methyl; R¹⁵ is a divalent alkylene moiety independently selected from C2H4, C3H6, and C4H8, and n represents an integer ranging from about 2 to about 150 in one aspect, from about 5 to about 120 in another aspect, and from about 10 to about 60 in a further aspect, (R¹⁵-0) can be arranged in a random or a block configuration; R¹⁶ is a substituted or unsubstituted alkyl selected from a C8-C30 linear alkyl, a C8-C30 branched alkyl, a C8-C30 carbocyclic alkyl, a C2-C30 alkyl-substituted phenyl, and an aryl-substituted C2-C30 alkyl.

[0065] Representative associative monomers under include lauryl polyethoxylated methacrylate (LEM), cetyl polyethoxylated methacrylate (CEM), cetearyl polyethoxylated methacrylate (CSEM), stearyl polyethoxylated (meth)acrylate, arachidyl polyethoxylated (meth)acrylate, behenyl polyethoxylated methacrylate (BEM), cerotyl polyethoxylated (meth)acrylate, montanyl polyethoxylated (meth)acrylate, melissyl polyethoxylated (meth)acrylate, phenyl polyethoxylated (meth)acrylate, nonylphenyl polyethoxylated (meth)acrylate, ω-tristyrylphenyl polyoxyethylene methacrylate, where the polyethoxylated portion of the monomer contains about 2 to about 150 ethylene oxide units in one aspect, from about 5 to about 120 in another aspect, from about 10 to about 60 in still another aspect, from 10 to 40 in a further aspect, and from 15 to 30 in a still further aspect; octyloxy polyethyleneglycol (8) polypropyleneglycol (6) (meth)acrylate, phenoxy polyethylene glycol (6) polypropylene glycol (6) (meth)acrylate, and nonylphenoxy polyethylene glycol polypropylene glycol (meth)acrylate.

[0066] The semi-hydrophobic monomers of the disclosed technology are structurally similar to the associative monomer described above but have a substantially non-hydrophobic end group portion. The semi-hydrophobic monomer has an ethylenically unsaturated end group portion (i) for addition polymerization with the other monomers of the disclosed technology; a polyoxyalkylene mid-section portion (ii) for imparting selective hydrophilic and/or hydrophobic properties to the product polymer and a semi-hydrophobic end group portion (iii). The unsaturated end group portion (i) supplying the vinyl or other ethylenically unsaturated end group for addition polymerization is preferably derived from an α,β-ethylenically unsaturated mono carboxylic acid. Alternatively, the end group portion (i) can be derived from an allyl ether residue, a vinyl ether residue or a residue of a nonionic urethane monomer.

[0067] The polyoxyalkylene mid-section (ii) specifically comprises a polyoxyalkylene segment, which is substantially similar to the polyoxyalkylene portion of the associative monomers described above. In one aspect, the polyoxyalkylene portions (ii) include polyoxyethylene, polyoxypropylene, and/or polyoxybutylene units comprising from about 2 to about 150 in one aspect, from about 5 to about 120 in another aspect, and from about 10 to about 60 in a further aspect of ethylene oxide, propylene oxide, and/or butylene oxide units, arranged in random or blocky sequences.

[0068] The semi-hydrophobic end group portion (iii) is a substantially non- hydrophobic end group selected from hydroxyl or a moiety containing 1 to 4 carbon atoms. Exemplary carbon atom containing semi-hydrophobic end groups include methyl, ethyl, propyl and butyl moieties.

[0069] In one aspect, the semi-hydrophobic monomer can be represented by the following formulas:

wherein R¹ is hydrogen or methyl; A is -CH₂C(0)0- -C(0)0-, -0-, -CH2O-, -NHC(0)NH- -C(0)NH-,-Ar-(CE₂)z-NHC(0)0-, -Ar-(CE₂)z-NHC(0)NH-, or -CH2CH2NHC(0)-; Ar is a divalent arylene (e.g. , phenylene); E is H or methyl; z is 0 or 1 ; k is an integer ranging from about 0 to about 30, and m is 0 or 1 , with the proviso that when k is 0, m is 0, and when k is in the range of 1 to about 30, m is 1 ; (R¹⁵-0)n is a polyoxyalkylene moiety, which can be a homopolymer, a random copolymer, or a block copolymer of C2-C4 oxyalkylene units, R¹⁵ is a divalent alkylene moiety selected from C2H4, C3H6, or C4H8, and combinations thereof; and n is an integer in the range of about 2 to about 150 in one aspect, from about 5 to about 120 in another aspect, and from about 10 to about 60 in a further aspect; R¹⁷ is selected from hydrogen and a linear or branched C1-C4 alkyl group (e.g., methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, and tert-butyl); and D represents a vinyl or an allyl moiety.

[0070] In one aspect, the semi-hydrophobic monomer can be represented by the following formulas:

CH2=C(R¹)C(0)0-(C2H₄0)a(C3H60)b-H

CH2=C(R¹)C(0)0-(C2H₄0)a(C3H60)b-CH3 wherein R¹ is hydrogen or methyl, and "a" is an integer ranging from 0 or 2 to about 120 in one aspect, from about 5 to about 45 in another aspect, and from about 10 to about 25 in a further aspect, and "b" is an integer ranging from about 0 or 2 to about 120 in one aspect, from about 5 to about 45 in another aspect, and from about 10 to about 25 in a further aspect, subject to the proviso that "a" and "b" cannot be 0 at the same time.

[0071] Examples of semi-hydrophobic monomers include polyethyleneglycol methacrylate available under the product names Blemmer^® PE-90 (R¹ = methyl, a = 2, b = 0), PE-200 (R¹ = methyl, a = 4.5, b = 0), and PE-350 (R¹ = methyl a = 8, b = 0,); polypropylene glycol methacrylate available under the product names Blemmer^® PP-1000 (R¹ = methyl, b = 4-6, a = 0), PP-500 (R¹ = methyl, a = 0, b = 9), PP-800 (R¹ = methyl, a = 0, b = 13); polyethyleneglycol polypropylene glycol methacrylate available under the product names Blemmer^® 50PEP-300 (R¹ = methyl, a = 3.5, b = 2.5), 70PEP-350B (R¹ = methyl, a = 5, b = 2); polyethyleneglycol acrylate available under the product names Blemmer^® AE-90 (R¹ = hydrogen, a = 2, b = 0), AE-200 (R¹ = hydrogen, a = 2, b = 4.5), AE-400 (R¹ = hydrogen, a = 10, b = 0); polypropyleneglycol acrylate available under the product names Blemmer^® AP-150 (R¹ = hydrogen, a = 0, b = 3), AP-400(R¹ = hydrogen, a = 0, b = 6), AP-550 (R¹ = hydrogen, a = 0, b = 9). Blemmer^® is a trademark of NOF Corporation, Tokyo, Japan.

[0072] Additional examples of semi-hydrophobic monomers include methoxypolyethyleneglycol methacrylate available under the product names Visiomer^® MPEG 750 MA W (R¹ = methyl, a = 17, b = 0), MPEG 1005 MA W (R¹ = methyl, a = 22, b = 0), MPEG 2005 MA W (R¹ = methyl, a = 45, b = 0), and MPEG 5005 MA W (R¹ = methyl, a = 1 13, b = 0) from Evonik Rohm GmbH, Darmstadt, Germany); Bisomer^® MPEG 350 MA (R¹ = methyl, a = 8, b = 0), and MPEG 550 MA (R¹ = methyl, a = 12, b = 0) from GEO Specialty Chemicals, Ambler PA; Blemmer^® PME-100 (R¹ = methyl, a = 2, b = 0), PME-200 (R¹ = methyl, a = 4, b = 0), PME400 (R¹ = methyl, a = 9, b = 0), PME-1000 (R¹ = methyl, a = 23, b = 0), PME-4000 (R¹ = methyl, a = 90, b = 0).

[0073] In one aspect, the semi-hydrophobic monomer can be represented by the following formulas:

CH2=CH-O-(CH2)d-O-(C3H₆O)e-(C2H₄O)f-H

CH2=CH-CH2-O-(C3H₆O)g-(C2H₄O)h-H wherein d is an integer of 2, 3, or 4; e is an integer in the range of from about 1 to about 10 in one aspect, from about 2 to about 8 in another aspect, and from about 3 to about 7 in a further aspect; f is an integer in the range of from about 5 to about 50 in one aspect, from about 8 to about 40 in another aspect, and from about 10 to about 30 in a further aspect; g is an integer in the range of from 1 to about 10 in one aspect, from about 2 to about 8 in another aspect, and from about 3 to about 7 in a further aspect; and h is an integer in the range of from about 5 to about 50 in one aspect, and from about 8 to about 40 in another aspect; e, f, g, and h can be 0 subject to the proviso that e and f cannot be 0 at the same time, and g and h cannot be 0 at the same time.

[0074] Semi-hydrophobic monomers are commercially available under the trade names Emulsogen^® R109, R208, R307, RAL109, RAL208, and RAL307 sold by Clariant Corporation; BX-AA-E5P5 sold by Bimax, Inc.; and combinations thereof. EMULSOGEN^® R109 is a randomly ethoxylated/propoxylated 1 ,4-butanediol vinyl ether having the empirical formula CH₂=CH-O(CH2)4O(C3H₆O)4(C2H₄O)ioH; Emulsogen^® R208 is a randomly ethoxylated/propoxylated 1 ,4-butanediol vinyl ether having the empirical formula CH2=CH-O(CH2)4O(C3H₆O)4(C2H₄O)2oH; Emulsogen^® R307 is a randomly ethoxylated/propoxylated 1 ,4-butanediol vinyl ether having the empirical formula CH2=CH-0(CH2)40(C3H₆0)4(C2H₄0)3oH; Emulsogen^® RAL109 is a randomly ethoxylated/propoxylated allyl ether having the empirical formula CH2=CHCH20(C3H₆0)4(C2H₄0)ioH; Emulsogen^® RAL208 is a randomly ethoxylated/propoxylated allyl ether having the empirical formula CH2=CHCH20(C3H₆0)4(C2H₄0)2oH; Emulsogen^® RAL307 is a randomly ethoxylated/propoxylated allyl ether having the empirical formula CH2=CHCH20(C3H60)4(C2H₄0)3oH; and BX-AA-E5P5 is a randomly ethoxylated/propoxylated allyl ether having the empirical formula CH2=CHCH20(C3H60)5(C2H₄0)5H .

[0075] In the associative and semi-hydrophobic monomers of the disclosed technology, the polyoxyalkylene mid-section portion contained in these monomers can be utilized to tailor the hydrophilicity and/or hydrophobicity of the polymers in which they are included. For example, mid-section portions rich in ethylene oxide moieties are more hydrophilic while mid-section portions rich in propylene oxide moieties are more hydrophobic. By adjusting the relative amounts of ethylene oxide to propylene oxide moieties present in these monomers the hydrophilic and hydrophobic properties of the polymers in which these monomers are included can be tailored as desired.

[0076] The amount of associative and/or semi-hydrophobic monomer utilized in the preparation of the polymers of the disclosed technology can vary widely and depends, among other things, on the final rheological and aesthetic properties desired in the polymer. When utilized, the one or more monomers selected from the associative and/or semi-hydrophobic monomers disclosed above can be utilized in amounts ranging from about 0. 1 to about 20 wt.%, or from about 0.5% to about 18%, or from about 1 %, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% 10% to about 15 wt.% (based on the total weight of the monounsaturated monomers in the polymerization medium) is utilized to prepare the polymer. lonizable Monomer

[0077] In one aspect of the disclosed technology, the crosslinked, nonionic, amphiphilic polymer compositions of the disclosed technology can be polymerized from a monomer composition including from about 0 to about 15.0 wt.% in one aspect, from about 0.1 to about 15 wt.% in another aspect, from about 0.5 to about 10 wt.% in still another aspect, from about 1 to about 8 wt. % in a further aspect, and from about 2 or 3 to about 5 wt.% in a still further aspect of an ionizable and/or ionized monomer, based on the weight of the total monomers, so long as the rheological properties of the composition are not deleteriously affected.

[0078] In another aspect, the amphiphilic polymer compositions of the disclosed technology can be polymerized from a monomer composition comprising less than 3 wt.% in one aspect, less than 1 wt.% in a further aspect, less than 0.5 wt.% in a still further aspect, less than 0.1 wt.% in an additional aspect, and less than 0.05 wt.% in a further aspect, of an ionizable and/or an ionized moiety, based on the weight of the total monomers.

[0079] Ionizable monomers include monomers having a base neutralizable moiety and monomers having an acid neutralizable moiety. Base neutralizable monomers include olefinically unsaturated monocarboxylic and dicarboxylic acids and their salts containing 3 to 5 carbon atoms and anhydrides thereof. Examples include (meth)acrylic acid, itaconic acid, maleic acid, maleic anhydride, and combinations thereof. Other acidic monomers include styrenesulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid (AMPS^® monomer), vinylsulfonic acid, vinylphosphonic acid, allylsulfonic acid, methallylsulfonic acid; and salts thereof.

[0080] Acid neutralizable monomers include olefinically unsaturated monomers which contain a basic nitrogen atom capable of forming a salt or a quaternized moiety upon the addition of an acid. For example, these monomers include vinylpyridine, vinylpiperidine, vinylimidazole, vinylmethylimidazole, dimethylaminomethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminomethyl (meth)acrylate and methacrylate, dimethylaminoneopentyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, and diethylaminoethyl (meth)acrylate. Crosslinking Monomer

[0081] In one aspect of the disclosed technology, the crosslinking monomer is an amphiphilic crosslinking agent. The amphiphilic crosslinking agent is utilized to polymerize covalent crosslinks into the amphiphilic polymer backbone. In some instances, conventional crosslinking agents can affect the volume expansion or swelling of micro-gel particles in fluids containing surfactants. For example, a high level of conventional crosslinking agent could provide a high yield stress, but the limited expansion of the micro-gels would result in undesirably high polymer use levels and low optical clarity. On the other hand, a low level of conventional crosslinking agents could give high optical clarity but low yield stress. It is desirable that polymeric micro-gels allow maximum swelling while maintaining a desirable yield stress, and it has been found that the use of amphiphilic crosslinking agents in place of, or in conjunction with conventional crosslinking agents can provide these benefits. In addition, it has been found that the amphiphilic crosslinking agent can be easily reacted into the amphiphilic polymer. Often, certain processing techniques, such as staging, can be required with conventional crosslinking agents to achieve the proper balance of optical clarity and yield stress. In contrast, it has been found that amphiphilic crosslinking agents can simply be added in a single stage with the monomer mixture during preparation.

[0082] In one aspect, exemplary amphiphilic crosslinking agents suitable for use with the present technology can include, but not be limited to, compounds such as those disclosed in US 2013/0047892 (published Feb. 28, 2013 to Palmer, Jr. et al.), represented by the following formulas:

(I)

where R²⁰=CH₃, CH2CH3, CeHs, or C14H29; n=1 , 2, or 3; x is 2-10, y is 0-200, z is 4-200, from about 5 to 60 in another aspect, and from about 5 to 40 in a further aspect; Z can be either SO3^" or PO3^2", and M⁺ is Na⁺, K⁺, NH₄ ⁺, or an alkanolamine such as, for example, monoethanolamine, diethanolamine, and triethanolamine;

where R²⁰=CH₃, CH2CH3, CeHs, or C14H29; n=1 , 2, 3; x is 2-10, y is 0-200, z is 4- 200, from about 5 to 60 in another aspect, and from about 5 to 40 in a further aspect;

where R²¹ is a C10-24 alkyl, alkaryl, alkenyl, or cycloalkyl,

CH2CH3, CeHs, or C14H29; x is 2-10, y is 0-200, z is 4-200, from about 5 to 60 in another aspect, and from about 5 to 40 in a further aspect; and R²² is H or Z^~ M⁺ Z can be either SO3^" or PO3^2", and M⁺ is Na⁺, K⁺, NH4⁺, or an alkanolamine such as, for example, monoethanolamine, diethanolamine, and triethanolamine.

[0083] In one embodiment, the amphiphilic crosslinking agent can be used in an amount ranging from about 0.01 to about 3 wt.% in one aspect, from about 0.05 to about 0.1 wt.% in another aspect, and from about 0.1 to about 0.9 wt.% in a further aspect, based on the total weight of the monounsaturated monomers utilized to prepare the nonionic, amphiphilic polymers of the disclosed technology. Stated another way, the amount of amphiphilic crosslinking agent and/or conventional crosslinking monomer discussed below can be calculated on the basis of parts by wt. (100% active material) per 100 parts by wt. (100% active material) of total monounsaturated monomers utilized to prepare the polymer of the disclosed technology.

[0084] In another embodiment, the amphiphilic crosslinking agent can contain an average of about 1 .5 or 2 unsaturated moieties and can be used in an amount ranging from about 0.01 to about 3 parts by wt.% in one aspect, from about 0.02 to about 1 parts by wt.% in another aspect, from about 0.05 to about 0.9 parts by wt.% in a further aspect, and from about 0.075 to about 0.5 wt.% parts by wt. in a still further aspect, and from about 0.1 to about 0.15 parts by wt.% in another aspect, based upon 100 parts by wt. of monounsaturated monomers utilized to prepare the nonionic, amphiphilic polymers of the disclosed technology.

[0085] In one aspect, the amphiphilic crosslinking agent is selected from compounds of formulas (IV) or (V) below:

where n is 1 or 2; z is 4 to 40 in one aspect, 5 to 38 in another aspect, and 10 to 20 in a further aspect; and R²² is H, S03^"M⁺ or PO3^"2 M⁺, and M is selected from Na, K, and NH₄;

[0086] The foregoing amphiphilic crosslinking agents conforming to formulas (I), (II), (III), (IV) and (V) are disclosed in U.S. Patent Application Publication No. US 2014/01 14006, the disclosure of which is herein incorporated by reference, and are commercially available under the E-Sperse™ RS Series trade name (e.g., product designations RS-1617, RS-1618, RS-1684) from Ethox Chemicals, LLC.

[0087] The amount of polyunsaturated amphiphilic crosslinking monomer utilized to crosslink the polymers of the disclosed technology ranges from about 0.1 to about 5 parts by weight or from about 0.1 , 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1 part to about 5 parts by weight (based on 100 parts by wt. of the monounsaturated monomers utilized to prepare the polymer).

[0088] In one embodiment, the crosslinking monomer can include a combination of an amphiphilic crosslinking agent and a conventional crosslinking agent. These are relatively low molecular weight polyunsaturated compounds (less than 300 Daltons). In one aspect, the conventional crosslinking agent is a polyunsaturated compound containing at least 2 unsaturated moieties. In another aspect, the conventional crosslinking agent contains at least 3 unsaturated moieties. Exemplary polyunsaturated compounds include di(meth)acrylate compounds such as ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1 ,3- butylene glycol di(meth)acrylate, 1 ,6-butylene glycol di(meth)acrylate, 1 ,6- hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1 ,9-nonanediol di(meth)acrylate, 2,2'-bis(4-(acryloxy-propyloxyphenyl)propane, and 2,2'-bis(4- (acryloxydiethoxy-phenyl)propane; tri(meth)acrylate compounds such as, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, and tetramethylolmethane tri(meth)acrylate; tetra(meth)acrylate compounds such as ditrimethylolpropane tetra(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, and pentaerythritol tetra(meth)acrylate; hexa(meth)acrylate compounds such as dipentaerythritol hexa(meth)acrylate; allyl compounds such as allyl (meth)acrylate, diallylphthalate, diallyl itaconate, diallyl fumarate, and diallyl maleate; polyallyl ethers of sucrose having from 2 to 8 allyl groups per molecule, polyallyl ethers of pentaerythritol such as pentaerythritol diallyl ether, pentaerythritol triallyl ether, and pentaerythritol tetraallyl ether, and combinations thereof; polyallyl ethers of trimethylolpropane such as trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, and combinations thereof. Other suitable polyunsaturated compounds include divinyl glycol, divinyl benzene, and methylenebisacrylamide.

[0089] In another aspect, suitable polyunsaturated monomers can be synthesized via an esterification reaction of a polyol made from ethylene oxide or propylene oxide or combinations thereof with unsaturated anhydride such as maleic anhydride, citraconic anhydride, itaconic anhydride, or an addition reaction with unsaturated isocyanate such as 3-isopropenyl-a-a- dimethylbenzene isocyanate.

[0090] Mixtures of two or more of the foregoing polyunsaturated compounds can also be utilized to crosslink the nonionic, amphiphilic polymers. In one aspect, the mixture of conventional unsaturated crosslinking monomer contains an average of 2 unsaturated moieties. In another aspect, the mixture of conventional crosslinking agents contains an average of 2.5 unsaturated moieties. In still another aspect, the mixture of conventional crosslinking agents contains an average of about 3 unsaturated moieties. In a further aspect, the mixture of conventional crosslinking agents contains an average of about 3.5 unsaturated moieties.

[0091] In one embodiment, the conventional crosslinking agent component can be used in an amount ranging from about 0.01 to about 0.5 parts by wt. in one aspect, from about 0.05 to about 0.4 parts by wt. in another aspect, and from about 0.1 to about 0.3 parts by wt. in a further aspect, based on 100 parts by wt. of the monounsaturated monomers utilized to prepare the nonionic, amphiphilic polymers of the disclosed technology.

[0092] In another embodiment of the disclosed technology, the conventional crosslinking agent component contains an average of about 3 unsaturated moieties and can be used in an amount ranging from about 0.01 to about 0.3 parts by wt. in one aspect, from about 0.02 to about 0.25 parts by wt. in another aspect, from about 0.05 to about 0.2 parts by wt. in a further aspect, and from about 0.075 to about 0.175 parts by wt. in a still further aspect, and from about 0.1 to about 0.15 parts by wt. in another aspect, based on 100 parts by wt. of the monounsaturated monomers utilized to prepare the nonionic, amphiphilic polymers of the disclosed technology.

[0093] In one aspect, the conventional crosslinking agent is selected from trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, pentaerythritol triallylether and polyallyl ethers of sucrose having 3 allyl groups per molecule.

[0094] In another aspect, the nonionic amphiphilic polymer can be crosslinked with a combination of a conventional crosslinking agent and an amphiphilic crosslinking agent. The conventional crosslinking agent and amphiphilic crosslinking agent can be used in a total amount ranging from about 0.01 to about 1 parts by wt. in one aspect, from about 0.05 to about 0.75 parts by wt. in another aspect, and from about 0.1 to about 0.5 parts by wt. in a further aspect, based on 100 parts by wt. of the monounsaturated monomers utilized to prepare the nonionic, amphiphilic polymers of the disclosed technology.

[0095] In one aspect, the combination of the conventional crosslinking agent and amphiphilic crosslinking agent can include conventional crosslinking agents selected from selected from trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, pentaerythritol triallylether and polyallyl ethers of sucrose having 3 allyl groups per molecule, and combinations thereof, and amphiphilic crosslinking agents selected from compounds of formula (III), (V), and combinations thereof. Amphiphilic Polymer Synthesis

[0096] The crosslinked, nonionic, amphiphilic polymer of the disclosed technology can be made using conventional free-radical emulsion polymerization techniques. The polymerization processes are carried out in the absence of oxygen under an inert atmosphere such as nitrogen. The polymerization can be carried out in a suitable solvent system such as water. Minor amounts of a hydrocarbon solvent, organic solvent, as well as mixtures thereof can be employed. To facilitate emulsification of the monomer mixture, the emulsion polymerization is carried out in the presence of at least one stabilizing surfactant. The polymerization reactions are initiated by any means which results in the generation of a suitable free-radical. Thermally derived radicals, in which the radical species is generated from thermal, homolytic dissociation of peroxides, hydroperoxides, persulfates, percarbonates, peroxyesters, hydrogen peroxide and azo compounds can be utilized. The initiators can be water soluble or water insoluble depending on the solvent system employed for the polymerization reaction.

[0097] The initiator compounds can be utilized in an amount of up to 30 wt.% in one aspect, 0.01 to 10 wt.% in another aspect, and 0.2 to 3 wt.% in a further aspect, based on the total weight of the dry polymer.

[0098] Exemplary free radical water soluble initiators include, but are not limited to, inorganic persulfate compounds, such as ammonium persulfate, potassium persulfate, and sodium persulfate; peroxides such as hydrogen peroxide, benzoyl peroxide, acetyl peroxide, and lauryl peroxide; organic hydroperoxides, such as cumene hydroperoxide and t-butyl hydroperoxide; organic peracids, such as peracetic acid, and water soluble azo compounds, such as 2,2'-azobis(tert-alkyl) compounds having a water solubilizing substituent on the alkyl group. Exemplary free radical oil soluble compounds include, but are not limited to 2,2'-azobisisobutyronitrile, and the like. The peroxides and peracids can optionally be activated with reducing agents, such as sodium bisulfite, sodium formaldehyde, or ascorbic acid, transition metals, hydrazine, and the like. [0099] In one aspect, azo polymerization catalysts include the Vazo^® free- radical polymerization initiators, available from DuPont, such as Vazo^® 44 (2,2'- azobis(2-(4,5-dihydroimidazolyl)propane), Vazo^® 56 (2,2'-azobis(2- methylpropionamidine) dihydrochloride), Vazo^® 67 (2,2'-azobis(2- methylbutyronitrile)), and Vazo^® 68 (4,4'-azobis(4-cyanovaleric acid)).

[0100] Optionally, the use of known redox initiator systems as polymerization initiators can be employed. Such redox initiator systems include an oxidant (initiator) and a reductant. Suitable oxidants include, for example, hydrogen peroxide, sodium peroxide, potassium peroxide, t-butyl hydroperoxide, t-amyl hydroperoxide, cumene hydroperoxide, sodium perborate, perphosphoric acid and salts thereof, potassium permanganate, and ammonium or alkali metal salts of peroxydisulfuric acid, typically at a level of 0.01 % to 3.0% by weight, based on dry polymer weight, are used. Suitable reductants include, for example, alkali metal and ammonium salts of sulfur-containing acids, such as sodium sulfite, bisulfite, thiosulfate, hydrosulfite, sulfide, hydrosulfide or dithionite, formadinesulfinic acid, hydroxymethanesulfonic acid, acetone bisulfite, amines such as ethanolamine, glycolic acid, glyoxylic acid hydrate, ascorbic acid, isoascorbic acid, lactic acid, glyceric acid, malic acid, 2-hydroxy-2-sulfinatoacetic acid, tartaric acid and salts of the preceding acids typically at a level of 0.01 % to 3.0% by weight, based on dry polymer weight, is used. In one aspect, combinations of peroxodisulfates with alkali metal or ammonium bisulfites can be used, for example, ammonium peroxodisulfate and ammonium bisulfite. In another aspect, combinations of hydrogen peroxide containing compounds (t- butyl hydroperoxide) as the oxidant with ascorbic or erythorbic acid as the reductant can be utilized. The ratio of peroxide-containing compound to reductant is within the range from 30: 1 to 0.05: 1 .

[0101] In one aspect, the polymerization can be carried out the presence of a chain transfer agent. Suitable chain transfer agents include, but are not limited to, thio- and disulfide containing compounds, such as C1 -C18 alkyl mercaptans, such as tert-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert- dodecyl mercaptan hexadecyl mercaptan, dodecyl mercaptan, octadecyl mercaptan; mercaptoalcohols, such as 2-mercaptoethanol, 2-mercaptopropanol; mercaptocarboxylic acids, such as mercaptoacetic acid and 3-mercaptopropionic acid; mercaptocarboxylic acid esters, such as butyl thioglycolate, isooctyl thioglycolate, dodecyl thioglycolate, isooctyl 3-mercaptopropionate, and butyl 3- mercaptopropionate; thioesters; C1-C18 alkyl disulfides; aryldisulfides; polyfunctional thiols such as trimethylolpropane-tris-(3-mercaptopropionate), pentaerythritol-tetra-(3-mercaptopropionate), pentaerythritol-tetra-(thioglycolate), pentaerythritol-tetra-(thiolactate), dipentaerythritol-hexa-(thioglycolate), and the like; phosphites and hypophosphites; C1-C4 aldehydes, such as formaldehyde, acetaldehyde, propionaldehyde; haloalkyl compounds, such as carbon tetrachloride, bromotrichloromethane, and the like; hydroxylammonium salts such as hydroxylammonium sulfate; formic acid; sodium bisulfite; isopropanol; and catalytic chain transfer agents such as, for example, cobalt complexes (e.g., cobalt (II) chelates).

[0102] The chain transfer agents are generally used in amounts ranging from 0.1 to 10 wt.%, based on the total weight of the monomers present in the polymerization medium.

[0103] The polymerization reaction can be carried out at temperatures ranging from 20 to 200°C in one aspect, from 50 to 150°C in another aspect, and from 60 to 100°C in a further aspect.

[0104] In emulsion polymerization processes it can be advantageous to stabilize the monomer/polymer droplets or particles by means of surface active auxiliaries. Typically, these are emulsifiers or protective colloids. Emulsifiers used can be anionic, nonionic, cationic or amphoteric. Examples of anionic emulsifiers are alkylbenzenesulfonic acids, sulfonated fatty acids, sulfosuccinates, fatty alcohol sulfates, alkylphenol sulfates and fatty alcohol ether sulfates. Examples of usable nonionic emulsifiers are alkylphenol ethoxylates, primary alcohol ethoxylates, fatty acid ethoxylates, alkanolamide ethoxylates, fatty amine ethoxylates, EO/PO block copolymers and alkylpolyglucosides. Examples of cationic and amphoteric emulsifiers used are quaternized amine alkoxylates, alkylbetaines, alkylamidobetaines and sulfobetaines. [0105] Examples of typical protective colloids are cellulose derivatives, polyethylene glycol, polypropylene glycol, copolymers of ethylene glycol and propylene glycol, polyvinyl acetate, polyvinyl alcohol), partially hydrolyzed polyvinyl alcohol), polyvinyl ether, starch and starch derivatives, dextran, polyvinylpyrrolidone, polyvinylpyridine, polyethyleneimine, polyvinylimidazole, polyvinylsuccinimide, polyvinyl-2-methylsuccinimide, polyvinyl-1 ,3-oxazolid-2- one, polyvinyl-2-methylimidazoline and maleic acid or anhydride copolymers. The emulsifiers or protective colloids are customarily used in concentrations from 0.05 to 20 wt.%, based on the weight of the total monomers.

[0106] In one aspect, the emulsion process can be conducted in the absence of a protective colloid. In this aspect, the emulsion process employs an amphiphilic additive. In accordance with one aspect of the present technology the amphiphilic additive is mixed into the polymerizable monomer mixture containing the amphiphilic crosslinking agent before introducing the monomer mixture into the polymerization medium. The monomer mixture (disperse phase) as well as the polymerization medium (continuous phase) is devoid of a protective colloid such as, for example, polyvinyl alcohol) and polyvinyl acetate) and/or a polymeric steric stabilizer. Surprisingly, it has been found that by mixing an amphiphilic additive with the polymerizable monomer mixture and removing the protective colloid from the emulsion polymerization medium the clarity and turbidity properties of surfactant compositions containing the resultant polymer product is improved.

[0107] The amphiphilic additives of the present technology are nonionic and contain at least one hydrophilic segment and at least two hydrophobic segments.

[0108] In one embodiment the amphiphilic additive of the present technology is represented by the formula:

(R)a— [ ^Q-b ^{A R23} (X) wherein Q represents a polyol residue; A represents a poly(ethylene glycol) residue; R is selected from a saturated and unsaturated Cio to C22 acyl group and a poly(propylene glycol) residue; R²³ is independently selected from H, a saturated and unsaturated C10 to C22 acyl radical and a poly(propylene glycol) residue; a is 0 or 1 ; b is 0 or 1 ; and c is a number from 1 to 4; subject to the proviso that when b is 0, a and c are 1 , and when b is 1 , a is 0 and R²³ is not a poly(propylene glycol) residue.

[0109] In one aspect of the disclosed technology, the amphiphilic additive is a polyethoxylated alkyl glucoside ester represented by the formula:

wherein R²³ is independently selected from H and a saturated and unsaturated C10-C22 acyl group; R²⁴ is selected from a C1 -C10 alkyl group; and the sum of w + x + y + z ranges from about 60 to about 150 in one aspect, from about 80 to about 135 in another aspect, and from about 90 to about 125 in a further aspect, and from about 100 to about 120 in a still further aspect; subject to the proviso that at no more than two of R²³ can be H at the same time.

[0110] In one aspect R²³ is an acyl residue of lauric acid, myristic acid, palmitic acid, palmitoleic acid, steric acid, isostearic acid, oleic acid, ricinoleic acid vaccenic acid, linoleic acid (alpha and gamma), arachidic acid, behenic acid, and mixtures thereof and R²⁵ is methyl.

[0111] Suitable polyethoxylated alkyl glucoside esters are commercially available under the trade names Glucamate™ LT (INCI Name: PEG-120 Methyl Glucose Trioleate (and) Propylene Glycol (and) Water), Glucamate™ VLT (INCI Name: PEG-120 Methyl Glucose Trioleate (and) Propanediol), and Glucamate™ DOE-120 (INCI Name: PEG-120 Methyl Glucose Dioleate).

[0112] In one aspect of the disclosed technology, the amphiphilic additive is selected from a poly(ethylene glycol) diester where poly(ethylene glycol) (PEG) is esterified with a saturated and unsaturated C10 to C22 fatty acid is represented by the formula:

wherein B is independently selected from a saturated and unsaturated C10 to C22 acyl radical; and n ranges from about 10 to about 120 in one aspect, from about 12 to about 1 10 in another aspect, and from about 15 to about 100 in a further aspect.

[0113] In one aspect B is an acyl residue of lauric acid, myristic acid, palmitic acid, palmitoleic acid, steric acid, isostearic acid, oleic acid, ricinoleic acid vaccenic acid, linoleic acid (alpha and gamma), arachidic acid, behenic acid, and mixtures thereof.

[0114] Exemplary PEG diesters include but are not limited to the laurate, palmitate, palmitoleate, stearate, isostearate, and oleate diesters of PEG-400, PEG-600, PEG-1000, PEG-2000, and PEG-4000.

[0115] In one aspect of the disclosed technology, the amphiphilic additive is a poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol)- block copolymer represented by the formula:

wherein r = t and range from about 5 to about 20 in one aspect, from about 6 to about 15 in another aspect, and from about 8 to about 14 in a further aspect; and s ranges from about 20 to about 30 in one aspect from about 21 to about 27 in another aspect and from about 23 to about 25 in a further aspect. [0116] In one aspect, the poly(propylene glycol)-block-poly(ethylene glycol)- block-poly(propylene glycol)-block copolymer has a number average molecular weight ranging from about 1500 to about 3500 Da.

[0117] The poly(propylene glycol)-block-poly(ethylene glycol)-block- poly(propylene glycol)-block copolymer contains from about 35 to about 60 in one aspect, from about 40 to about 55 wt.% in another aspect, and from about 45 to about 50 wt.% in still another aspect of poly(ethylene glycol). Suitable poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol)- block copolymers are marketed under the Pluronic™ 10R5 and Pluronic™ 17R4 trade names by BASF Corporation, Florham Park, NJ.

[0118] The amount of amphiphilic additive that is mixed with the polymerizable monomer mixture ranges from about 1 to about 15 parts by wt. in one aspect, from about 2 to about 10 parts by wt. in another aspect, and from about 3 to about 6 parts by wt. in still another aspect, based upon 100 parts by wt. of the monounsaturated monomers utilized to prepare the nonionic, amphiphilic polymers of the disclosed technology.

[0119] The emulsion process can be conducted in in a single reactor or in multiple reactors as is well-known in the art. The monomers can be added as a batch mixture or each monomer can be metered into the reactor in a staged process. A typical mixture in emulsion polymerization comprises water, monomer(s), an initiator (usually water-soluble) and an emulsifier. The monomers may be emulsion polymerized in a single-stage, two-stage or multistage polymerization process according to well-known methods in the emulsion polymerization art. In a two-stage polymerization process, the first stage monomers are added and polymerized first in the aqueous medium, followed by addition and polymerization of the second stage monomers. The aqueous medium optionally can contain an organic solvent. If utilized, the organic solvent is less than about 5 wt.% of the aqueous medium. Suitable examples of water- miscible organic solvents include, without limitation, esters, alkylene glycol ethers, alkylene glycol ether esters, lower molecular weight aliphatic alcohols, and the like. [0120] To facilitate emulsification of the monomer mixture, the emulsion polymerization is carried out in the presence of at least one stabilizing surfactant. The term "stabilizing surfactant" is used in the context of surfactants employed to facilitate emulsification. In one embodiment, the emulsion polymerization is carried out in the presence of stabilizing surfactant (active weight basis) ranging in the amount of about 0.2% to about 5% by weight in one aspect, from about 0.5% to about 3% in another aspect, and from about 1 % to about 2% by weight in a further aspect, based on a total monomer weight basis. The emulsion polymerization reaction mixture also includes one or more free radical initiators which are present in an amount ranging from about 0.01 % to about 3% by weight based on total monomer weight. The polymerization can be performed in an aqueous or aqueous alcohol medium. Stabilizing surfactants for facilitating the emulsion polymerization include anionic, nonionic, amphoteric, and cationic surfactants, as well as reactive derivatives thereof, and mixtures thereof. By "reactive derivatives thereof" it is meant surfactants, or mixtures of surfactants, having on average less than one reactive moiety. Most commonly, anionic and nonionic surfactants can be utilized as stabilizing surfactants as well as mixtures thereof.

[0121] Suitable anionic surfactants for facilitating emulsion polymerization are well known in the art and include, but are not limited to (C6-Cie) alkyl sulfates, (C6-C18) alkyl ether sulfates (e.g., sodium lauryl sulfate and sodium laureth sulfate), amino and alkali metal salts of dodecylbenzenesulfonic acid, such as sodium dodecyl benzene sulfonate and dimethylethanolamine dodecylbenzenesulfonate, sodium (C6-C16) alkyl phenoxy benzene sulfonate, disodium (C6-C16) alkyl phenoxy benzene sulfonate, disodium (C6-C16) di-alkyl phenoxy benzene sulfonate, disodium laureth-3 sulfosuccinate, sodium dioctyl sulfosuccinate, sodium di-sec-butyl naphthalene sulfonate, disodium dodecyl diphenyl ether sulfonate, disodium n-octadecyl sulfosuccinate, phosphate esters of branched alcohol ethoxylates, and the like, as well as reactive derivatives thereof.

[0122] Nonionic surfactants suitable for facilitating emulsion polymerizations are well known in the polymer art, and include, without limitation, linear or branched C8-C30 fatty alcohol ethoxylates, such as capryl alcohol ethoxylate, lauryl alcohol ethoxylate, myristyl alcohol ethoxylate, cetyl alcohol ethoxylate, stearyl alcohol ethoxylate, cetearyl alcohol ethoxylate, sterol ethoxylate, oleyl alcohol ethoxylate, and, behenyl alcohol ethoxylate; alkylphenol alkoxylates, such as octylphenol ethoxylates; and polyoxyethylene polyoxypropylene block copolymers, and the like, as well as reactive derivatives thereof. Additional fatty alcohol ethoxylates suitable as non-ionic surfactants are described below. Other useful nonionic surfactants include C8-C22 fatty acid esters of polyoxyethylene glycol, ethoxylated mono- and diglycerides, sorbitan esters and ethoxylated sorbitan esters, C8-C22 fatty acid glycol esters, block copolymers of ethylene oxide and propylene oxide, and combinations thereof, as well as reactive derivatives thereof. The number of ethylene oxide units in each of the foregoing ethoxylates can range from 2 and above in one aspect, and from 2 to about 150 in another aspect.

[0123] Optionally, other emulsion polymerization additives and processing aids which are known in the emulsion polymerization art, such as solvents, protective colloids, buffering agents, chelating agents, inorganic electrolytes, biocides, and pH adjusting agents can be included in the polymerization system.

[0124] In one aspect a two-stage emulsion polymerization reaction is utilized to prepare the polymers of the present technology. A mixture of the monounsaturated monomers, the amphiphiphilic crosslinking agent and the protective colloid or amphiphilic additive is added to a first reactor under inert atmosphere to a solution of emulsifying surfactant (e.g., anionic surfactant) in water. The monomer mixture is devoid of a protective colloid and/or a polymeric steric stabilizer such as polyvinyl alcohol or polyvinyl acetate) if the amphiphilic additive is utilized. The contents of the first reactor are agitated to prepare a monomer emulsion (disperse phase). To a second reactor equipped with an agitator, an inert gas inlet, and feed pumps are added under inert atmosphere a desired amount of water and additional anionic surfactant (dispersing medium or continuous phase). The contents of the second reactor are heated with mixing agitation. After the contents of the second reactor reaches a temperature in the range of about 55 to 98°C, a free radical initiator is injected into the aqueous surfactant solution, and the monomer emulsion from the first reactor is gradually metered into the second reactor over a period typically ranging from about one half to about four hours. The reaction temperature is controlled in the range of about 45 to about 95°C. After completion of the monomer addition, an additional quantity of free radical initiator can optionally be added to the second reactor, and the resulting reaction mixture is typically held at a temperature of about 45 to 95°C for a time period sufficient to complete the polymerization reaction to obtain the polymer emulsion.

[0125] In one aspect, the crosslinked, nonionic, amphiphilic polymers of the disclosed technology are selected from an emulsion polymer polymerized from a monomer mixture comprising from about 20 to about 60 wt.% of at least one Ci- C5 hydroxyalkyl (meth)acrylate; from about 10 to about 50 wt.% of at least one C1 -C5 alkyl (meth)acrylate; from about 0.1 , 1 , 5, or 7 to about 15 wt.% of at least one associative and/or a semi-hydrophobic monomer (wherein all monomer weight percentages are based on the total weight of the monounsaturated monomers); and from about 0.01 to about 5 parts by wt. in one aspect, from about 0.1 to about 3 parts by wt. in another aspect, and from about 0.5 to about 1 parts by wt. in a further aspect of at least one amphiphilic crosslinker (based upon 100 parts by wt. of the monounsaturated monomers utilized to prepare the polymer).

[0126] In one aspect, the crosslinked, nonionic, amphiphilic polymers of the disclosed technology are selected from an emulsion polymer polymerized from a monomer mixture comprising from about 20 to 50 wt.% of hydroxyethyl methacrylate; from about 10 to about 30 wt.% ethyl acrylate; from about 10 to about 35 wt.% butyl acrylate; from about 1 to about 10 or 15 wt.% of at least one associative and/or semi-hydrophobic monomer (wherein all monomer weight percentages are based on the weight of the total monomers); and from about 0.01 to about 5 parts by wt. in one aspect, from about 0.1 to about 3 parts by wt. in another aspect, and from about 0.5 to about 1 parts by wt. in a further aspect of at least one amphiphilic crosslinker (based on 100 parts by wt. of the monounsaturated monomers utilized to prepare the polymer), and from about 1 to about 15 parts by wt. in one aspect, from about 2 to 10 parts by wt. in another aspect.

[0127] In one aspect, the crosslinked, nonionic, amphiphilic polymers of the disclosed technology are selected from an emulsion polymer polymerized from a monomer mixture comprising from about 40 to 50 wt.% of hydroxyethyl methacrylate; from about 10 to about 25 wt.% ethyl acrylate; from about 20 to about 30 wt.% butyl acrylate; from about 5 or 6 to about 15 wt.% of at least one associative monomer selected from lauryl polyethoxylated (meth)acrylate, cetyl polyethoxylated (meth)acrylate, cetearyl polyethoxylated (meth)acrylate, stearyl polyethoxylated (meth)acrylate, arachidyl polyethoxylated (meth)acrylate, behenyl polyethoxylated (meth)acrylate, cerotyl polyethoxylated (meth)acrylate, montanyl polyethoxylated (meth)acrylate, melissyl polyethoxylated (meth)acrylate, where the polyethoxylated portion of the monomer contains about 2 to about 50 ethylene oxide units (wherein all monomer weight percentages are based on the weight of the total monomers); and from about 0.01 to about 5 parts by wt. in one aspect, from about 0.1 to about 3 parts by wt. in another aspect, and from about 0.5 to about 1 parts by wt. in a further aspect of at least one polyunsaturated amphiphilic crosslinker (based on 100 parts by wt. of the monounsaturated monomers utilized to prepare the polymer).

Detersive Surfactants

[0128] The fatty acid soap compositions of the present technology can include an optional synthetic detersive surfactant (syndet) selected from anionic, amphoteric, zwitterionic, nonionic, and combinations thereof.

[0129] The anionic surfactant can be any of the anionic surfactants known or previously used in the art of aqueous surfactant compositions. Suitable anionic surfactants include but are not limited to alkyl sulfates, alkyl ether sulfates, alkaryl sulfonates, alkyl succinates, alkyl sulfosuccinates, N-acyl amino acid surfactants such as taurates (e.g., potassium cocoyl taurate, potassium methyl cocoyl taurate, sodium caproyl methyl taurate, sodium cocoyl taurate, sodium lauroyl taurate, sodium methyl cocoyl taurate, sodium methyl lauroyl taurate, sodium methyl myristoyl taurate, sodium methyl oleoyl taurate, sodium methyl palmitoyl taurate, sodium methyl stearoyi taurate), glutamates (e.g., di-potassium capryloyl glutamate, di-potassium undecylenoyl glutamate, di-sodium capryloyl glutamate, di-sodium cocoyi glutamate, di-sodium lauroyl glutamate, di-sodium stearoyi glutamate, di-sodium undecylenoyl glutamate, potassium capryloyl glutamate, potassium cocoyi glutamate, potassium lauroyl glutamate, potassium myristoyl glutamate, potassium stearoyi glutamate, potassium undecylenoyl glutamate, sodium capryloyl glutamate, sodium cocoyi glutamate, sodium lauroyl glutamate, sodium myristoyl glutamate, sodium olivoyl glutamate, sodium palmitoyl glutamate, sodium stearoyi glutamate, sodium undecylenoyl glutamate), glycinates (e.g., sodium palmitoyl glycinate, sodium lauroyl glycinate, sodium cocoyi glycinate, sodium myristoyl glycinate, potassium lauroyl glycinate, potassium cocoyi glycinate, sodium stearoyi glycinate), alanine and alaninates (e.g., cocoyi methyl β-alanine, lauroyl β-alanine, lauroyl methyl β-alanine, myristoyl β-alanine, potassium lauroyl methyl β-alanine, sodium cocoyi alaninate, sodium cocoyi methyl β-alanine, sodium myristoyl methyl β-alanine), sacosinates (e.g., potassium lauroyl sarcosinate, potassium cocoyi sarcosinate, sodium cocoyi sarcosinate, sodium lauroyl sarcosinate, sodium myristoyl sarcosinate, sodium palmitoyl sarcosinate), aspartates (e.g., sodium lauroyl aspartate, sodium myristoyl aspartate, sodium cocoyi aspartate, sodium caproyl aspartate, di-sodium lauroyl aspartate, di-sodium myristoyl aspartate, di-sodium cocoyi aspartate, di-sodium caproyl aspartate, potassium lauroyl aspartate, potassium myristoyl aspartate, potassium cocoyi aspartate, potassium caproyl aspartate, di-potassium lauroyl aspartate, di-potassium myristoyl aspartate, di- potassium cocoyi aspartate, di-potassium caproyl aspartate), alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, alkylamino acids, alkyl peptides, carboxylic acids, alkyl isethionates, and alpha-olefin sulfonates, especially their sodium, potassium, magnesium, ammonium and mono-, di- and triethanolamine salts. The alkyl groups generally contain from 8 to 18 carbon atoms and may be unsaturated. The alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates may contain from 1 to 10 ethylene oxide and/or propylene oxide units per molecule in one aspect, and from about 1 to about 4 ethylene oxide units per molecule in another aspect. [0130] Examples of suitable anionic surfactants include sodium and ammonium lauryl ether sulfate (ethoxylated with 1 , 2, and 3 moles of ethylene oxide), sodium trideceth sulfate (ethoxylated with 1 , 2, 3, and 4 moles of ethylene oxide), sodium, ammonium, and triethanolamine lauryl sulfate, disodium laureth sulfosuccinate, sodium cocoyl isethionate, sodium C12-14 olefin sulfonate, sodium laureth-6 carboxylate, sodium C12-15 pareth sulfate, sodium methyl cocoyl taurate, sodium dodecylbenzene sulfonate, sodium cocoyl sarcosinate, and triethanolamine monolauryl phosphate.

[0131] Amphoteric and zwitterionic surfactants are those compounds which have the capacity of behaving either as an acid or a base. These surfactants can be any of the surfactants known or previously used in the art of aqueous surfactant compositions. Suitable materials include but are not limited to alkyl betaines, alkyl amidopropyl betaines, alkyl sulphobetaines, alkyl glycinates, alkyl carboxyglycinates, alkyl amphopropionates, alkyl amidopropyl hydroxysultaines, acyl taurates and acyl glutamates wherein the alkyl and acyl groups have from 8 to 18 carbon atoms. Examples include cocamidopropyl betaine, sodium cocoamphoacetate, cocamidopropyl hydroxysultaine, and sodium cocamphopropionate.

[0132] The nonionic surfactant can be any of the nonionic surfactants known or previously used in the art of aqueous surfactant compositions. Suitable nonionic surfactants include but are not limited to aliphatic (C6 to Cis) primary or secondary linear or branched chain acids, alcohols or phenols, alkyl ethoxylates, alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), block alkylene oxide condensate of alkyl phenols, alkylene oxide condensates of alkanols, ethylene oxide/propylene oxide block copolymers, semi-polar nonionics (e.g., amine oxides and phosphine oxides), as well as alkyl amine oxides. Other suitable nonionics include mono or di alkyl alkanolamides and alkyl polysaccharides, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol esters, polyoxyethylene acids, and polyoxyethylene alcohols. Examples of suitable nonionic surfactants include coco mono or diethanolamide, coco diglucoside, alkyl polyglucoside, cocamidopropyl and lauramine oxide, polysorbate 20, ethoxylated linear alcohols, cetearyl alcohol, lanolin alcohol, stearic acid, glyceryl stearate, PEG-100 stearate, and oleth 20.

[0133] Other surfactants which can be utilized in the present invention are set forth in more detail in WO 99/21530, U.S. Patent No. 3,929,678, U.S. Patent No. 4,565,647, U.S. Patent No. 5,720,964, and U.S. Patent No. 5,858,948. Other suitable surfactants are described in McCutcheon's Emulsifiers and Detergents (North American and International Editions, by Schwartz, Perry and Berch) which is hereby fully incorporated by reference.

[0134] In one embodiment of the disclosed technology, the amount of surfactant can vary widely if present. The amounts (active basis) which are often utilized generally range from about 0 or 1 to about 15 wt.% in one aspect, from about 2 to about 12 wt.% in another aspect, from about 2.5 to about 10 wt.% in a further aspect, and from about 5 to about 8 wt.% in still further aspect, based upon the total weight of the composition, subject to the proviso that the total amount of surfactant employed in the composition is less than the amount of fatty acid salt soap utilized in the composition.

[0135] In other embodiments, the amount of optional surfactant utilized in the composition can be based on the amount of fatty acid soap present in the liquid cleansing composition and can be expressed as the weight ratio of fatty acid soap to surfactant. In one aspect of the disclosed technology, the ratio of fatty acid soap to surfactant ranges from about 1 : 1 to about 5:1 , in another aspect the soap to surfactant ratio ranges from about 1 .5: 1 to about 3:1 , and in a further aspect the soap to surfactant ratio ranges from about 2: 1 to about 2.5: 1 (all ratios based on a wt./wt. basis).

[0136] In one aspect of the disclosed technology the surfactant is selected from a mixture of an anionic surfactant(s) and amphoteric surfactant(s). In one aspect, the anionic surfactant is selected from at least one alkyl ether sulfate conforming to the formula:

R(OCH₂CH₂)_mOSO₃ CA⁺ wherein R is C10 to C16 alkyl; m is an integer of 1 , 2, 3 or 4; and CA is a cation selected from an alkali metal (e.g., sodium, potassium) or ammonium. In one aspect the anionic surfactant is sodium laureth sulfate or sodium trideceth sulfate containing 1 to 4 moles of ethoxylation.

[0137] In one aspect, the amphoteric surfactant is selected from an alkyl betaine and/or an amido alkyl betaine conforming to the respective formulas:

R¹ N⁺R²R³(CH₂)_nC(0)0^" wherein R¹ is a Ce to C22 alkyl group; R² and R³ independently represent a Ci to C4 alkyl group or a hydroxy Ci to C4 alkyl group; and n is 1 or 2.

R⁴C(0)NH(CH₂)_pN⁺R⁵R⁶(CH₂)_qC(0)0^" wherein R⁴ is a C9 to C21 alkyl group; R⁵ and R⁶ independently represent Ci to C4 alkyl group or a hydroxyl Ci to C4 alkyl group; p is an integer ranging from about 1 to about 6; and q is 1 or 2.

[0138] In one aspect, the mixture of anionic surfactant and amphoteric surfactant comprises sodium laureth sulfate (with 1 to 3 moles of ethoxylation) with cocamidopropyl betaine. In one aspect, the surfactant comprises sodium trideceth sulfate with cocamidopropyl betaine.

Water

[0139] Water is also an ingredient in the compositions according to embodiments of the disclosed technology. In one aspect, the liquid cleansing compositions described herein are in the form of non-emulsion liquids in which water is the principal carrier/diluent/carrier. Taking into account the desired amounts (wt.%) of the other active components utilized to formulate the soap compositions of the disclosed technology, the quantity of water employed in the compositions will always correspond to a weight percentage needed to bring the total weight of the composition to 100 (i.e., quantity sufficient (q.s.) to 100). In another aspect, the amount of water can range from about 25 to about 89.5 wt.%, in a further aspect from about 35 to about 85 wt.%, in a still further aspect from about 40 to about 80 wt.%, in an additional aspect from about 40 to about 75 wt.%, in a still additional aspect from about 50 to about 70 wt.%, and a further additional aspect from about 55 to about 65 wt.%, based on the total weight of the composition. pH Adjusting Agents

[0140] The pH of the cleansing compositions of the disclosed technology is above 7 in one aspect, from about 7.5 to about 10.5 in another aspect, from about 7.8 to about 9.8 in still another aspect, from about 8 to about 9.5 in a further aspect, and from about 8.2 to about 9.2 in a still further aspect. Because of the base saponification of the precursor animal and vegetable derived fatty acids and/or base neutralization of free fatty acids to obtain the fatty acid salt soap component of the disclosed technology, the soap compositions will typically be in the basic pH range, i.e. above about pH 7. However, it may be desired or necessary to adjust the pH of the final composition to the desired pH value. A sufficient amount of a pH adjusting agent (base and/or acid) can be added to the soap composition of the disclosed technology to attain the desired pH.

[0141] Many types of alkaline (basic) pH adjusting agents can be used, including inorganic and organic bases, and combinations thereof. Examples of inorganic bases include but are not limited to the ammonium and alkali metal hydroxides (especially sodium and potassium), and alkali metal salts of inorganic acids, such as sodium borate (borax), sodium phosphate, sodium pyrophosphate, and the like; and mixtures thereof. Examples of organic bases include, but are not limited to, triethanolamine (TEA), diisopropanolamine, triisopropanolamine, aminomethyl propanol, dodecylamine, cocamine, oleamine, morpholine, triamylamine, triethylamine, tetrakis(hydroxypropyl)ethylenediamine, L-arginine, aminomethyl propanol, tromethamine (2-amino 2-hydroxymethyl-1 ,3- propanediol), and PEG-15 cocamine.

[0142] In one aspect, the acidic pH adjusting agents are selected from an organic acid, such as citric acid, acetic acid, alpha-hydroxy acids, beta-hydroxy acids, salicylic acid, lactic acid, fumaric acid, glutamic acid, glycolic acid, tartaric acid, natural fruit acids, or combinations thereof. In addition, inorganic acids, for example, hydrochloric acid, nitric acid, sulfuric acid, sodium bisulfate, sulfamic acid, phosphoric acid, and combinations thereof can be utilized. Mixtures of organic acids and inorganic acids are also contemplated.

Humectant

[0143] The fatty acid liquid soap composition of the disclosed technology optionally includes at least one humectant. Humectants are defined as materials that absorb or release water vapor, depending on the relative humidity of the environment, (Harry's Cosmeticology, Chemical Publishing Company Inc., 1982 p. 266). Suitable humectants that can be included in the soap compositions include, but are not limited to, allantoin; pyrrolidonecarboxylic acid and its salts; hyaluronic acid and salts thereof; sorbic acid and salts thereof; urea, lysine, arginine, cystine, guanidine, and other amino acids; polyhydroxy alcohols such as glycerin, propylene glycol, hexylene glycol, hexanetriol, ethoxydiglycol, dimethicone copolyol, and sorbitol, and the esters thereof; polyethylene glycol; glycolic acid and glycolate salts (e.g. ammonium and quaternary alkyl ammonium); chitosan; aloe-vera extracts; algae extract; honey and derivatives thereof; inositol; lactic acid and lactate salts (e.g. ammonium and quaternary alkyl ammonium); sugars and starches; sugar and starch derivatives (e.g. alkoxylated glucose); DL-panthenol; magnesium ascorbyl phosphate, arbutin, kojic acid, lactamide monoethanolamine; acetamide monoethanolamine; and the like, and mixtures thereof. Humectants also include the C3 to C6 diols and triols, such as glycerin, propylene glycol, hexylene glycol, hexanetriol, and the like, and mixtures thereof. Ethoxylated methyl glucose ethers containing an average of 5 to 30 moles of ethoxylation, such as, for example, those available under the INCI names Methyl Glucose-10 and Methyl Glucose-20, are suitable. When utilized, humectants typically comprise from about 1 wt.% to about 10 wt.% of the total weight of the soap compositions of the disclosed technology. In another aspect the amount can range from about 2 wt.% to about 8 wt. %, and in a further aspect from about 3 wt. % to about 5 wt. % of the total weight of the soap composition.

Emollient

[0144] The fatty acid soap composition of the disclosed technology optionally includes at least one emollient. An emollient is defined as a substance which regulates the rate and quantity of water uptake by the skin (Handbook of Cosmetic Science and Technology, Elsevier Science Publishing, 1993, p. 175). Suitable emollients include mineral oil; vegetable oil; hydrogenated vegetable oil, stearic acid; fatty alcohols such as cetyl alcohol, cetearyl alcohol, myristyl alcohol, behenyl alcohol, and lauryl alcohol, cetyl acetate in acetylated lanolin alcohol, benzoate esters such as C12 to C15 alkyl benzoates, isostearyl benzoate, dicaprylyl maleate, petrolatum, lanolin, coco butter, shea butter, beeswax and esters thereof, ethoxylated fatty alcohol esters such as ceteareth-20, oleth-5, and ceteth-5, alkoxylated fatty acid esters such as polyethylene glycol 400 propoxylated monolaurate, avocado oil or glycerides, sesame oil or glycerides, safflower oil or glycerides, sunflower oil or glycerides, and other mono-, di- and triglycerides of natural vegetable and botanical oils, such as, for example, caprylic triglyceride, capric triglyceride, caprylic/capric triglyceride, and caprylic/capric/lauric triglyceride, Guerbet esters such as G-20, G-36, G-38, and G-66 marketed by Lubrizol Advanced Materials, Inc., botanical seed oils, volatile silicone oils, non-volatile emollients, and the like; and mixtures thereof.

[0145] Suitable non-volatile emollients include fatty acid and fatty alcohol esters, highly branched hydrocarbons, and the like, and mixtures thereof. Such fatty acid and fatty alcohol esters include decyl oleate, butyl stearate, octyl stearate, myristyl myristate, octyldodecyl stearoylstearate, octylhydroxystearate, di-isopropyl adipate, isopropyl myristate, isopropyl palmitate, ethyl hexyl palmitate, isodecyl neopentanoate C12 to C15 alcohol benzoate, diethyl hexyl maleate, PPG-14 butyl ether and PPG-2 myristyl ether propionate, cetearyl octanoate, and the like, and mixtures thereof. Suitable highly branched hydrocarbons include isohexadecane and the like, and mixtures thereof. [0146] Suitable volatile emollients include the volatile silicones, such as cyclic or linear polydimethylsiloxanes, and the like. The number of silicon atoms in cyclic silicones can range from about 3 to about 7 in one aspect of the invention, and in another aspect from 4 to 5. Exemplary volatile silicones, both cyclic and linear, are available from Dow Corning Corporation as Dow Corning 344, 345, and 200. The linear volatile silicones typically have viscosities of less than about 5 cP at 25°C, while the cyclic volatile silicones typically have viscosities of less than about 10 cP at 25°C. "Volatile" means that the silicone has a measurable vapor pressure. A description of volatile silicones can be found in Todd and Byers, "Volatile Silicone Fluids for Cosmetics", Cosmetics and Toiletries, Vol. 91 , January 1976, pp. 27-32.

[0147] Other emollient silicones include polydimethylsiloxane gums, aminosilicones, phenylsilicones, polydimethyl siloxane, polydiethylsiloxane, polymethylphenylsiloxane, polydimethylsiloxane gums, polyphenyl methyl siloxane gums, amodimethicone, trimethylsilylamodimethicone, diphenyl- dimethyl polysiloxane gums, and the like.

[0148] The emollients, if present (alone or in combination), range from about 1 wt.% to about 15 wt.% in one aspect, from about 2 wt.% to about 10 wt.% in another aspect, and from about 3 wt.% to about 5 wt.% in a further aspect, based of the total weight of the soap composition.

Other Optional Components

[0149] The fatty acid soap compositions of the invention can contain a variety of other conventional optional components suitable for rendering the cleansing compositions more desirable. Such optional components are well known to those skilled in the art of formulating soap compositions and include, but not limited to, one or more preservatives, one or more thickening agents, one or more viscosity adjusting agents, one or more skin conditioners, one or more antibacterial agents, one or more fragrances, one or more colorants, and one or more insoluble materials.

[0150] Suitable preservatives and antimicrobial agents, if present, include polymethoxy bicyclic oxazolidine, methyl paraben, propyl paraben, ethyl paraben, butyl paraben, benzoic acid and the salts of benzoic acid, e.g., sodium benzoate, benzyltriazole, DMDM hydantoin (also known as 1 ,3-dimethyl-5,5- dimethyl hydantoin), imidazolidinyl urea, phenoxyethanol, phenoxyethylparaben, methylisothiazolinone, methylchloroisothiazolinone, benzoisothiazolinone, triclosan, sorbic acid, salicylic acid salts, and the like, and mixtures thereof. Preservatives typically comprise about 0.01 wt. % to about 1 .5 wt. % of the total wt. of the personal care compositions of the present invention.

[0151] Suitable thickening agents may be any natural and/or synthetic agent (or combination thereof) to obtain enhanced thickening properties. The person skilled in the art will readily select a proper thickening agent(s) and amounts(s) thereof to obtain the desired rheology. Non-limiting examples of natural thickening agents are tree & shrub exudates (karaya gum, tragacanth gum, gum Arabic, gum ghatti), seed extracts (guar gum, cassia gum, locust been gum, tamarind seed), seaweed extracts (carrageenan, alginates, agar), fruit extracts (pectins, waxes), grains & roots (corn starch, potato starch, etc), microbial polysaccharides (Xanthan gum, dextran), modified natural products (cellulose derivatives such as hydropropyl cellulose, methylcellulose, hydroxypropyl methylcellulose, cellulose gum, etc.); and hydrophobically modified ethoxylated methyl glucosides, such as PEG 120 methyl glucose dioleate, PEG-120 methyl glucose trioleate, and PEG-20 methyl glucose sesquistearate, available from Lubrizol Advanced Materials, Inc., under the trade names, Glucamate™ DOE- 120, Glucamate™ LT and VLT, and Glucamate™ SSE-20, respectively, are also suitable as thickening agents. Non-limiting examples of synthetic thickening agents include the polyethylene glycols (PEG) having 5 to 200 glycol units, such as, for example, those available under the INCI names PEG- 6, PEG-8, PEG-12, PEG-20, PEG-30, PEG-32, PEG-75, PEG-90, PEG-100 and PEG-200; acrylic/methacrylic acid homopolymers and copolymers, such as, for example, those sold under the trade names Carbopol^® 934, Carbopol 940, Carbopol 941 , Carbopol 980, Carbopol 981 , Carbopol 2984, Carbopol 5984, Carbopol ETD 2050, Carbopol Ultrez 10, Carbopol Ultrez 30 (INCI name: Carbomer); Carbopol 1342, Carbopol 1382, Carbopol ETD 2020, Carbopol Ultrez 20, Carbopol Ultrez 21 , Pemulen™ TR-1 and Pemulen TR-2 (INCI name: Acrylates/Cio-C3o Alkyl Acrylate Crosspo!ymer); Carbopo! Aqua SF-1 (INCI name: Acry!ates Copolymer); manufactured and sold by Lubrizol Advanced Materials, Inc., Cleveland, OH; acrylamide homopolymers and copolymers; polymers prepared from 2-acrylamido-2-methylpropanesulfonic acid (AMPS^® monomer),

[0152] Another class of synthetic thickeners suitable for use includes the hydrophobically modified alkali-swellable emulsion polymers, commonly referred to as (HASE) polymers. Typical HASE polymers are free radical addition polymers polymerized from pH sensitive or hydrophilic monomers (e.g. , acrylic acid and/or methacrylic acid, 2-acrylamido-2-methylpropane sulfonic acid), hydrophobic monomers (e.g. , C1-C30 alkyl esters of acrylic acid and/or methacrylic acid, acrylonitrile, styrene), an "associative monomer", and an optional crosslinking monomer. The associative monomer comprises an ethylenically unsaturated polymerizable end group, a non-ionic hydrophilic midsection that is terminated by a hydrophobic end group. The non-ionic hydrophilic midsection comprises a polyoxyalkylene group, e.g. , polyethylene oxide, polypropylene oxide, or mixtures of polyethylene oxide/polypropylene oxide segments. The terminal hydrophobic end group is typically a Ce-C-w aliphatic moiety. Exemplary aliphatic moieties are selected from linear and branched alkyl substituents, linear and branched alkenyl substituents, carbocyclic substituents, aryl substituents, aralkyl substituents, arylalkyl substituents, and alkylaryl substituents. In one aspect, associative monomers can be prepared by the condensation (e.g. , esterification or etherification) of a polyethoxylated and/or polypropoxylated aliphatic alcohol (typically containing a branched or unbranched Ce-C-w aliphatic moiety) with an ethylenically unsaturated monomer containing a carboxylic acid group (e.g. , acrylic acid, methacrylic acid), an unsaturated cyclic anhydride monomer (e.g. , maleic anhydride, itaconic anhydride, citraconic anhydride), a monoethylenically unsaturated monoisocyanate (e.g. , α,α-dimethyl-m-isopropenyl benzyl isocyanate) or an ethylenically unsaturated monomer containing a hydroxyl group (e.g. , vinyl alcohol, allyl alcohol). Polyethoxylated and/or polypropoxylated aliphatic alcohols are ethylene oxide and/or propylene oxide adducts of a monoalcohol containing the Ce-C-w aliphatic moiety. Non-limiting examples of alcohols containing a Ce-C-w aliphatic moiety are capryl alcohol, iso-octyl alcohol (2-ethyl hexanol), pelargonic alcohol (1 -nonanol), decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, cetyl alcohol, cetearyl alcohol (mixture of C16-C18 monoalcohols), stearyl alcohol, isostearyl alcohol, elaidyl alcohol, oleyl alcohol, arachidyl alcohol, behenyl alcohol, lignoceryl alcohol, ceryl alcohol, montanyl alcohol, melissyl, lacceryl alcohol, geddyl alcohol, and C2-C20 alkyl substituted phenols (e.g., nonyl phenol), and the like.

[0153] Exemplary HASE polymers are disclosed in U.S. Patent Nos. 3,657, 175; 4,384,096; 4,464,524; 4,801 ,671 ; and 5,292,843, which are herein incorporated by reference. In addition, an extensive review of HASE polymers is found in Gregory D. Shay, Chapter 25, "Alkali-Swellable and Alkali-Soluble Thickener Technology A Review", Polymers in Aqueous Media - Performance Through Association, Advances in Chemistry Series 223, J. Edward Glass (ed.), ACS, pp. 457-494, Division Polymeric Materials, Washington, DC (1989), the relevant disclosures of which are incorporated herein by reference. Commercially available HASE polymers are sold under the trade names, Aculyn^® 22 (INCI Name: Acrylates/Steareth-20 Methacrylate Copolymer), Aculyn^® 44 (INCI Name: PEG-150/Decyl Alcohol/SMDI Copolymer), Aculyn 46^® (INCI Name: PEG-150/Stearyl Alcohol/SMDI Copolymer), and Aculyn^® 88 (INCI Name: Acrylates/Steareth-20 Methacrylate Crosspolymer) from Rohm & Haas, and Novethix™ L-10 (INCI Name: Acrylates/Beheneth-25 Methacrylate Copolymer) from Lubrizol Advanced Materials, Inc. Other thickeners are commercially available under the INCI designations Ammonium Acryloyldimethyltaurate/VP Copolymer, Ammonium Acryloyl

Dimethyltaurate/Carboxyethyl Acrylate Crosspolymer, and Ammonium Acryloyldimethyltaurate/Beheneth-25 Methacrylate Crosspolymer.

[0154] If utilized, the thickeners can comprise from about 0.01 wt. % to about 5 wt. % of the total weight of the personal care composition, in another aspect the amount ranges from about 0.1 wt. % to about 3 wt. %, and in a further aspect from about 0.1 wt. % to about 2.0 wt. % of the total weight of the personal care composition. [0155] Viscosity adjusting agents are used in cosmetics to enhance the fluidity of products without a significant lowering of the concentration of the active constituents. Suitable viscosity adjusting agents if present include organic and inorganic compounds, and combinations thereof. Examples of organic compounds include ethanol, isopropyl alcohol, sorbitol, propylene glycol, diethylene glycol, triethylene glycol, dimethyl ether, butylene glycol, and the like, and mixtures thereof. Examples of inorganic compounds include sodium chloride, sodium sulfate, potassium chloride, potassium nitrate, and mixtures thereof. If utilized the viscosity adjusting agents typically comprise from about 0.1 wt. % to about 20 wt.% in one aspect, and from about 1 wt.% to about 5 wt.% of the total weight of the fatty acid soap composition of the disclosed technology.

[0156] Skin and/or hair conditioning polymers include quaternized guar gum (INCI name Guar Hydroxypropyltrimonium Chloride), quaternized cassia gum (INCI name Cassia Hydroxypropyltrimonium Chloride), such as, for example, products available under the Sensomer™ trade name from Lubrizol Advanced Materials, Inc., quaternized cellulosics, polyquaternium-4, polyquaternium-6, polyquaternium-7, polyquaternium-22, polyquaternium-39, polyquaternium-52, silicone quaternium-8 (dimethicone copolyol quaternized with an alkylamido dimethylamine, polyquaternium 10, polyquaternium 1 1 , polyquaternium 39, polyquaternium 44, and the like, and mixtures thereof. Such suitable conditioning agents if present typically comprise about 0.01 wt. % to about 3 wt. % of the total wt. of the composition of the present invention.

[0157] Examples of suitable antibacterial agents which can be used herein include, but are not limited to, 2-hydroxy-4,2',4'-trichlorodiphenylether (TCS), 2,6- dimethyl-4-hydroxychlorobenzene (PCMX),3,4,4'-trichlorocarbanilide (TCC), 3- trifluoromethyl-4,4'-dichlorocarbanilide (TFC), 2,2'-dihydroxy-3,3',5,5',6,6'- hexachlorodiphenylmethane, 2,2'-dihydroxy-3,3',5,5'- tetrachlorodiphenylmethane, 2,2'-dihydroxy-3,3',dibromo-5,5'- dichlorodiphenylmethane, 2-hydroxy4,4'-dichlorodiphenylether, 2-hydroxy-3,5',4- tribromodiphenylether, 1 -hydroxyl-4-methyl-6-(2,4,4-trimethylpentyl)-2(1 H)- pyridinone (Octopirox), salts of 2-pyridinethiol-1 -oxide, salicylic acid, and other organic acids. Other suitable antibacterial agents are described in U.S. Patent. Nos. 3,835,057; 4,714,653; and 6,488,943. The disclosed soap composition can include from about 0.001 wt.% to about 2 wt.% in one aspect, from about 0.01 wt.% to about 1 .5 wt.% in another aspect, and from about 0.1 wt.% to about 1 wt.% in a further aspect of the antibacterial agent(s), based on the total weight of the composition.

[0158] The fragrance substances that can be used in the soap compositions of the disclosed technology include natural and synthetic fragrances, perfumes, scents, and essences and any other substances and mixtures which emit a fragrance. As the natural fragrances, there are those of vegetable origin, such as oil extracts from flowers (e.g., lily, lavender, rose, jasmine, neroli, ylang- ylang), stems and leaves (geranium, patchouli, petitgrain, peppermint), fruits (aniseed, coriander, fennel, needle juniper), fruit skin (bergamot, lemon, orange, mace), roots angelica, celery, cardamom, costus, iris, sweet flag), woods (pine tree, sandalwood, guaiacum wood, cedar, rosewood, cinnamon), herbs and grasses (tarragon, lemongrass, sage, thyme), needles and twigs (spruce, pine, European red pine, stone pine), and resins and balsam (galbanum, elemi, benzoin, myrrh, frankincense, opopanax), and those of animal origin, such as musk, civet, castoreum, ambergris, or the like, and mixtures thereof.

[0159] Examples of synthetic fragrances and perfumes are the aromatic esters, ethers, aldehydes, ketones, alcohols, and hydrocarbons including, but are not limited to, benzyl acetate, phenoxyethyl isobutylate, p-tert- butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styralyl propionate, and benzyl salicylate; benzylethyl ether; straight chain alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial, and bougeonal; ionone compounds, a-isomethyl ionone, and methyl cedryl ketone; anethole, citronellol, eugenol, isoeugenol, geraniol, lavandulol, nerolidol, linalool, phenylethyl alcohol, and terpineol, alpha-pinene, terpenes (e.g., limonene), and balsams, and mixtures thereof.

[0160] The amount of fragrance material(s) that can be utilized will depend on the preference of the skilled formulator. In one aspect, the amount of fragrance material can range from about 0.05 wt.% to about 3 wt. %, in another aspect from about 0.1 wt.% to about 1 .5 wt.%, in still another aspect from about 0.3 wt.% to about 1 wt.%, and in a further aspect from about 0.5 wt.% to 0.75 wt.%, based on the weight of the total soap composition.

[0161] Colorants include water soluble dyes such as copper sulfate, iron sulfate, water-soluble sulfopolyesters, rhodamines, natural dyes, for instance carotene and beetroot juice, methylene blue, caramel, the disodium salt of tartrazine and the disodium salt of fuschin, and mixtures thereof. The amount of colorant(s) employed in the soap composition will depend on the aesthetic preference of the skilled formulator.

[0162] Insoluble materials include materials that impart pearlescent and other aesthetic visual, sensory and/or beneficial effects to the soap composition. Some formulations are opacified by deliberately incorporating pearlescent materials therein to achieve a cosmetically attractive pearl-like appearance, known as pearlescence. A detailed discussion of the effect is found in the article "Opacifiers and pearling agents in shampoos" by Hunting, Cosmetic and Toiletries, Vol. 96, pages 65 to 78 (July 1981 ), incorporated herein by reference.

[0163] The pearlescent material includes titanium dioxide coated mica, iron oxide coated mica, ethylene glycol monostearate, ethylene glycol distearate, polyethylene glycol distearate, bismuth oxychloride coated mica, myristyl myristate, guanine, glitter (polyester or metallic), and mixtures thereof. Other pearlescent materials can be found in U.S. Patent No. 4,654,207 and U.S. Patent No. 5,019,376, herein incorporated by reference.

[0164] The amount of the pearlescent material can generally be used in amounts of from about 0.05% to about 10% and desirably from about 0.15% to about 3% by wt. based upon the total wt. of the composition.

[0165] In addition to the above generally insoluble compounds, numerous other optional substantially insoluble compounds which require stabilization can be utilized in the composition. Examples of such other insoluble compounds include titanium dioxide; pumice; calcium carbonate, talc, potato starch, tapioca starch, jojoba beads, polyethylene beads, walnut shells, loofah, apricot seeds; almond meal, corn meal, paraffin, oat bran/oat hulls, gelatin beads, alginate beads, stainless steel fibers, iron oxide pigments, air bubbles, mica coated iron oxides, kaolin clay, salicylic acid, zinc oxide, zeolite, styrofoam beads, phosphates, silica, and the like. Other generally insoluble compounds include teatree powder, microsponges, Confetti (a trademark of united guardian company), talc, beeswax, and the like. The amount of the various insoluble compounds requiring stabilization will vary depending upon its purpose, desired end result, and efficacy thereof. Hence amounts can vary widely, but frequently will be within a general range of from about 0.1 % to about 20% by wt. based upon the total wt. of the soap composition.

[0166] The fatty acid salt soap-based compositions according to the disclosed technology can be dispensed, for example, onto a user's hand, directly onto the area of a body to be treated, or onto a cloth, such as a washcloth, sponge, loofa or a towelette, as a means to transport the composition to specified area(s) of the human body. In other aspects of the disclosed technology, the composition may be impregnated into carrier means such as a towelette or wipe. When the composition is impregnated into carrier means, the carrier means may be sealed in a container that does not react adversely with the composition prior to use and that helps prevent the composition from being exposed to the environment prior to use.

[0167] The fatty acid salt soap compositions formulated according to the presently disclosed technology may be applied to different parts of the body as rinse-off and/or leave-on applications. For example, such compositions may be applied to a part of a body and then be allowed to dry in place (e.g., a leave-on application, such as a lotion or cream), as it may be non-toxic to users. In other embodiments, the area to which the composition is applied may be toweled or blotted, thereby allowing the composition to evaporate or otherwise sink into the applied area. In further embodiments, the composition may be applied to an area and then rinsed off after a predetermined time. The area of application can be hydrated (pre-wetted) prior to application of the composition. The composition can be applied with a cloth, bath sponge (e.g., luffa or loofah), hand, or the like. In some examples, the composition may be applied by rubbing the composition onto an area (e.g., using mechanical action with a hand, sponge, or the like) for a period ranging from one second to two minutes such as, e.g., a period ranging from approximately fifteen seconds to approximately one minute. The mechanical rubbing action helps to create foam, helps loosen and remove debris from the hair and skin, and helps the composition penetrate an afflicted area(s). The composition can be applied as disclosed above to selected areas afflicted with a pruritus including winter itch or can be applied as a personal care body cleanser during showering or bathing. The personal care cleansing composition can be formulated as a shampoo, body wash, shower gel, facial wash or scrub, hand cleanser, or make-up remover.

[0168] The soap cleansing composition can be applied to an afflicted area (with mechanical rubbing) of the body and/or the scalp and allowed to reside on the area (residence time) for greater than approximately 5 seconds before being rinsed off such as, e.g., greater than approximately 20 seconds in one aspect, greater than approximately 25 seconds in another aspect, greater than 30 seconds in still another aspect, greater than 1 minute in a further aspect, greater than approximately 5 minutes in a still further aspect. Recommended residence time ranges can range from approximately 10 seconds to approximately 5 minutes in one aspect, from approximately 20 seconds to approximately 1 minute in another aspect, from approximately 1 minute to approximately 2 minutes in still another aspect, or other lengths of time, as clinically appropriate. The foregoing residence times and residence time ranges can include the amount of time that the composition is actively rubbed on the skin of the user and the amount of time that the composition resides on the skin of the patient without being actively rubbed.

[0169] In some applications, a user can apply the composition to a skin area larger than an area specifically targeted for treatment (e.g., an afflicted area). For example, the user may apply the composition to the skin of an entire limb that includes the area specifically targeted for treatment, to the skin of substantially the entire body (e.g., an entire body wash), or to other suitable portions of a body. Such broader application of the composition may enhance the effectiveness of the composition on the area specifically targeted for treatment (e.g., an area or portion of the body already afflicted with the pruritus condition), by preventively treating adjacent of areas of the skin from developing a pruritus condition.

[0170] Compositions according to the disclosure may be applied to a part of the body with any suitable frequency. In some examples, the compositions may be used comparatively infrequently such as, for example, once per month, once per week, twice per week. Alternatively, the compositions may be applied more frequently such as, for example, at least twice per week, at least once per day, at least twice per day, or the like. In some examples, the skin of the user can be hydrated (e.g., wetted with water) before applying the soap-based composition.

Ingredient Descriptions and Abbreviations

Example 1

Monomer composition = EA/n-BA/HEMA/BEM (35/15/45/5) wt.

[0171] An emulsion polymer was prepared as follows. A monomer premix was made by mixing 140 grams of Dl water, 5 grams of E-Sperse^® RS-1618 amphiphilic crosslinker, 175 grams of (EA), 75 grams of (n-BA), 225 grams of (HEMA) and 33.3 grams of (BEM). Initiator A was made by mixing 2.86 grams of TBHP in 40 grams of Dl water. Reductant A was prepared by dissolving 0.13 grams of erythorbic acid in 5 grams of Dl water. Reductant B was prepared by dissolving 2.0 grams of erythorbic acid in 100 grams of Dl water. A 3-liter reactor was charged with 800 grams of Dl water, 10 grams of 40% AOS and 25 grams of Selvol^® 502 PVA. The contents of the reactor were heated to 70°C under a nitrogen blanket with agitation. After holding the reactor contents at 70°C for one hour, initiator A was added to the reactor followed by addition of reductant A. After about 1 minute, the monomer premix was metered into the reaction vessel over a period of 180 minutes. About 3 minutes after the start of monomer premix introduction, reductant B was metered to the reactor over a period of 210 minutes. The reaction temperature was kept at 65°C. After completion of reductant B feed, the temperature of the reaction vessel contents was maintained at 65°C for 60 minutes. The reactor contents were then cooled to 60°C. A solution of 1 .79 grams of TBHP and 0.13 grams of 40% AOS in 15 grams of Dl water was added to the reactor. After 5 minutes, a solution of 1 .05 grams of erythorbic acid in 15 grams of Dl water was added to the reactor. The reactor contents were maintained at 60°C. After 30 minutes, a solution of 1 .79 grams of TBHP and 0.13 grams of 40% AOS in 15 grams of Dl water was added to the reactor. After 5 minutes, a solution of 1 .05 grams of erythorbic acid in 15 grams of Dl water was added to the reactor. The reactor contents were maintained at 60°C for about 30 minutes. Then, the reactor was cooled to room temperature and filtered through 100 micron filter cloth. The pH of the resulting emulsion was adjusted to 4.5 with ammonium hydroxide. The polymer product had a solids content of 30.4%, a viscosity of 21 cps, and a particle size of 1 19 nm.

Example 2

Monomer composition = HEMA/n-BA/EA/B EM/AM^* (45/25/15/15/0.8^*) (wt.% total monomers) (^*AM = 0.8 wt.% based on total monounsaturated monomer wt.).

[0172] An emulsion polymer was prepared as follows. A monomer premix was prepared by mixing 200 grams of D. I. water, 4 grams of E-Sperse RS-1618 amphiphilic crosslinker, 28.41 grams of Glucamate™ VLT ethoxylated MEG triester amphiphilic additive, 75 grams of EA, 125 grams of n-BA, 225 grams of HEMA, 100 grams of BEM. Initiator A was prepared by dissolving 4 grams of Azo VA-086 in 40 grams of D.I. water. Initiator B was prepared by dissolving 0.75 grams of Azo VA-086 in 100 grams of D. I. water. A 3-liter reactor was charged with 770 grams of D. I. water, 6.67 grams of SLS and then the contents were heated to 90°C under a nitrogen blanket with agitation. Initiator A was then added to the reactor. After 3 minutes, the monomer premix was metered into the reaction vessel over a period of 120 minutes. About 1 minute after the start of monomer premix feed, initiator B was metered into the reactor over a period of 150 minutes. The reaction temperature was then maintained at 87°C. After completion of the initiator B feed, the temperature of the reaction vessel contents was reduced to 85°C for 60 minutes. The reactor was then cooled to 49°C. A solution of 0.61 grams of TBHP and 0.38 grams of SLS in 16.8 grams of D. I. water was added to the reactor. After 5 minutes, a solution of 0.59 grams of erythorbic acid in 16.8 grams of D. I. water was added to the reactor. The reactor contents were maintained at 49°C. After 30 minutes, a solution of 0.64 grams of TBHP and 0.38 grams of SLS in 16.8 grams of D. I. water was added to the reactor. After 5 minutes, a solution of 0.59 grams of erythorbic acid in 16.8 grams of D. I. water was added to the reactor. The reactor contents were maintained at 49°C for 30 minutes. The reactor contents were then cooled to the room temperature (approximately 22°C) and filtered through 100 micron mesh cloth. The resulting emulsion had a pH 3.1 , a solids content of 29.1 wt.%, a viscosity of 125 mPa-s, and an average particle size of 82 nm.

Example 3

[0173] A liquid soap composition is prepared utilizing the ingredients in Table 1 . Table 1

methylisothiazolinone, Rohm and Haas

[0174] Part A is prepared by dissolving potassium hydroxide in deionized water and heating the composition to 80°C. Part B is separately prepared by adding glycerin and the rheology modifier to deionized (D. I.) water while mixing. The fatty acids (ingredient Nos. 3, 4, and 5) are added to the glycerin/rheology modifier/water mixture with agitation and the temperature is raised to 80°C. Once the fatty acids melt and are homogeneously mixed, the other Part B ingredients are added to the composition. Part A is added to Part B while the temperature is maintained at 80°C. The Part AB composition is mixed for 30 to 60 minutes. Upon attaining a homogeneous mixture, the Part AB composition is allowed to cool at ambient room temperature. Upon cooling to 40°C, ingredient No. 9 is added to the Part AB. The formulation is cooled under agitation to ambient room temperature.

Example 4

[0175] A liquid soap/surfactant blend composition is prepared utilizing the listed in Table 2. Table 2

methylisothiazolinone, Rohm and Haas

[0176] Part A is prepared by dissolving potassium hydroxide in deionized water and heated to 80°C. The ingredients of Part B are slowly heated with mixing until melted and then further heated until the temperature reaches 80°C. Parts A and B are combined with mixing. Part C is added to the combined Part AB composition which is maintained at 80°C and mixed until dissolved. While the combined Part ABC composition cools at ambient room temperature, the ingredients of Parts D and E are added in numerical order with thorough mixing. The viscosity of the liquid soap composition is adjusted with the addition of 10 g of sodium chloride. The initial pH, viscosity and yield values of the composition are measured. Following the measurement of the viscosity and yield value at the initial pH, the pH is sequentially increased with potassium hydroxide (85% solution) to a pH of 9.5 and then sequentially reduced by the addition of citric acid (25% solution) to a pH of 8.6. The initial viscosity and yield values as well as the viscosity and yield values following the sequential increase and reduction of the pH of the liquid soap composition are reported in the table below.

Claims

What is claimed is:

1 . A method for the treatment or mitigation of a pruritic skin condition comprising applying to the scalp and/or skin a composition comprising:

a) a liquid soap comprising at least one fatty acid salt;

b) a crosslinked amphiphilic nonionic polymer prepared from a monomer mixture comprising:

i. 35% to about 55%, or from about 40% to about 50% or from about 42% to about 48%, or from about 44% to about 46% by weight of at least one Ci to Cs hydroxyalkyl ester of (meth)acrylic acid (based on the total weight of the monounsaturated monomers);

ii. from about 10% to about 50%, or from about 10% to about 40%, or from about 12% to about 35%, or from about 15 to about 25 % by weight of at least one Ci to Cs alkyl ester of (meth)acrylic acid;

iii. from about 0.1 % to about 20%, or from about 0.5% to about 18%, or from about 1 %, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10% to about 15% by weight of an associative monomer (wherein all monomer weight percentages under i, ii, and iii are based on the total weight of the monounsaturated monomers); and

iv. from about 0.1 , 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1 to about 5 parts by wt. of at least one polyunsaturated crosslinker monomer (based on 100 parts by wt. of the monounsaturated monomers);

c) water; and

d) optionally at least one surfactant other than a).

2. A method of claim 1 wherein said at least one fatty acid salt is present in an amount ranging from about 10 to about 35 wt.% in one aspect, from about 12 to about 30 wt. % in another aspect, from about 15 to about 25 wt.% in a further aspect, and from about 18 to about 20 wt. % in a still further aspect (based on the total wt. of the composition).

3. A method of any one of the preceding claims wherein said polymer (on an active basis) is present in an amount ranging from about 0.5 to about 5 wt.%, or, from about 0.6 to about 4 wt.%, or from about 1 to about 3 wt.%, or from about 1 .5 to about 2 wt.% (based on the total wt. of the composition).

4. A method of any one of the preceding claims wherein said at least one surfactant (on an active basis) is present in an amount ranging from about 0 to about 15 wt.%, or from about 1 to about 12 wt.%, or from about 2.5 to about 10 wt.%, or from about 5 to about 8 wt.% in a still further aspect (based on the total wt. of the composition).

5. The method of any one of the preceding claims wherein the pH of said at least one composition ranges from about 7.5 to about 10.5 in one aspect, from about 7.8 to about 9.8 in another aspect, from about 8 to about 9.5 in a further aspect, and from about 8.2 to about 9.2 in a still further aspect.

6. A method of any one of the preceding claims wherein said at least one salt of a fatty acid is selected from the alkali metal and/or ethanolamine salt of a Ce to C22 fatty acid.

7. A method of any one of the preceding claims wherein said fatty acid is derived from vegetable oil, seed oil, and mixtures thereof.

8. A method of any one of the preceding claims wherein said fatty acid salt is derived from a fatty acid selected from octanoic acid, decanoic acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, steric acid, isostearic acid, nonadecanoic acid, arachidic acid, behenic acid, and mixtures thereof.

9. A method of any one of the preceding claims wherein said fatty acid salt is an alkali metal or alkanol ammonium salt of said fatty acid.

10. A method of any one of the preceding claims wherein said at least surfactant is selected from an anionic surfactant, an amphoteric surfactant, a nonionic surfactant, and mixtures thereof.

1 1 . A method of any one of the preceding claims wherein said anionic surfactant is selected from alkyl sulfates, alkyl ether sulfates, alkyl monoglyceryl ether sulfates, alkyl sulfonates, alkylaryl sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkyl sulfosuccinamates, alkyl amidosulfosuccinates, alkyl carboxylates, alkyl amidoethercarboxylates, alkyl succinates, N-acyl amino acids, alkyl phosphates, or combinations thereof.

12. A method of any one of the preceding claims wherein said amphoteric surfactant is selected from alkyl betaines, alkylamino betaines, and alkylamido betaines, and the corresponding sulfobetaines.

13. A method of any one of the preceding claims wherein said at least one surfactant is selected from a combination of an anionic surfactant and an amphoteric surfactant.

14. A method of any one of the preceding claims wherein said at least one surfactant is selected from a combination of an anionic surfactant and an amphoteric surfactant wherein the wt. ratio of anionic surfactant to amphoteric surfactant ranges from about 1 : 1 to about 10: 1 .

15. A method of any one of the preceding claims wherein said composition further comprises a component selected from a humectant, an emollient, a hair conditioner, a skin conditioner, a fragrance agent, an antibacterial agent, a preservative, a colorant, a botanical extract, a chelating agent, a pH adjusting agent, a thickening agent, and combinations thereof.

16. A method of any one of the preceding claims wherein said composition comprises: a) from about 10 to about 20 wt.% of at least one salt of a C12 to C22 fatty acid;

b) from about 0.5 to about 5 wt.% a crosslinked nonionic amphiphilic emulsion polymer prepared from a monomer mixture comprising:

i. about 45% by weight of 2-hydroxyethyl methacrylate;

ii. about 20.5% by weight of ethyl acrylate;

iii. about 27.5% by weight of butyl acrylate;

iv. about 7% by weight of behenyl ethoxylated methacrylate (based on 100 parts by wt. of the monounsaturated monomers utilized to prepare the polymer);

v. from about 0.1 to about 1 part by wt. of at least one polyunsaturated amphiphilic crosslinker monomer (based on 100 parts by wt. of the monounsaturated monomers utilized to prepare the polymer);

c) water; and

d) optionally at least one surfactant other than a).

17. A method of any one of claims 1 to 15 wherein said composition comprises:

a) from about 10 to about 20 wt.% of at least one salt of a C12 to C22 fatty acid;

i. about 45% by weight of 2-hydroxyethyl methacrylate;

ii. about 15% by weight of ethyl acrylate;

iii. about 25% by weight of butyl acrylate;

v. from about 0.5 to about 2 parts by wt. of at least one polyunsaturated amphiphilic crosslinker monomer (based on 100 parts by wt. of the monounsaturated monomers utilized to prepare the polymer); c) water; and d) optionally at least one surfactant other than a).

18. A method of any one of the preceding claims wherein said at least one polyunsaturated amphiphilic crosslinker monomer is represented by the structure:

where R²¹ is a C10-24 alkyl, alkaryl, alkenyl, or cycloalkyl,

CH2CH3, CeHs, or C14H29; x is 2-10, y is 0-200, z is 4-200, from about 5 to 60 in another aspect, and from about 5 to 40 in a further aspect; and R²² is H or Z^~ M⁺ Z can be either SO3^" or PO3^2", and M⁺ is Na⁺, K⁺, NH₄ ⁺, or an alkanolamine such as, for example, monoethanolamine, diethanolamine, and triethanolamine.

19. A method of any one of the preceding claims wherein said at least one polyunsaturated amphiphilic crosslinker monomer is represented by the structure:

where n is 1 or 2; z is 4 to 40, or 5 to 38, or 10 to 20; and R²² is H, S03^"M⁺ or PO3^"2 M⁺, and M is selected from Na, K, and NH₄

20. A method of any one of the preceding claims wherein said at least one polyunsaturated amphiphilic crosslinker monomer is represented by the structure:

A method of any one of the preceding claims wherein said monomer mixture further comprises a protective colloid selected from polyvinyl acetate, polyvinyl alcohol), partially hydrolyzed polyvinyl alcohol), and mixtures thereof.

22. A method of any one of the preceding claims wherein said monomer mixture further comprises an amphiphilic additive selected from a polyethoxylated alkyl glucoside ester represented by the formula:

wherein R²³ is independently selected from H and a saturated and unsaturated C10-C22 acyl group; R²⁴ is selected from a C1 -C10 alkyl group; and the sum of w + x + y + z ranges from about 60 to about 150, or from about 80 to about 135, or from about 90 to about 125, or from about 100 to about 120; subject to the proviso that at no more than two of R²³ can be H at the same time.

23. A method of any one of the preceding claims wherein said fatty acid salt is derived from a fatty acid selected from lauric acid, myristic acid, palmitic acid, steric acid, isostearic acid, or combinations thereof.

24. A method of any one of the preceding claims wherein said fatty acid salt is derived from a mixture of fatty acids selected from lauric acid, myristic acid, and palmitic acid.

25. A method of any one of the preceding claims wherein said fatty acid salt is derived from a mixture of fatty acids selected from lauric acid, myristic acid, and steric acid.

26. A method of any one of the preceding claims wherein said fatty acid salt is derived from a mixture of fatty acids selected from lauric acid, myristic acid, and, isostearic acid.

27. A method of any one of the preceding claims wherein said fatty acid salt is an alkali metal or alkanol ammonium salt of said fatty acid.

28. A method of any one of the preceding claims wherein said composition has a pH ranging from about 7.5 to about 10.5 in one aspect, from about 7.8 to about 9.8 in another aspect, from about 8 to about 9.5 in a further aspect, and from about 8.2 to about 9.2 in a still further aspect.

29. A method of any one of the preceding claims wherein the ratio of anionic surfactant to amphoteric surfactant ranges from about 1 :1 to about 10: 1 .

30. A method of any one of the preceding claims wherein said anionic surfactant is from an alkyl ether sulfate containing form about 1 to 3 moles of ethoxylation and said amphoteric surfactant is selected from an alkylamido betaine.

31 . A method of any one of the preceding claims comprising hydrating the scalp and/or skin prior to said application.

32. A method of any one of the preceding claims comprising rubbing the at least one composition after application to the scalp and/or skin to create lather.

33. A method of any one of the preceding claims comprising allowing the at least one composition to reside on the scalp and/or skin for a period greater than about 20 seconds in one aspect, greater than about 25 seconds in another aspect, and greater than about 30 seconds in a further aspect.

34. A method of any one of the preceding claims comprising rinsing the scalp and/or skin subsequent to said application.

35. A method of any one of the preceding claims wherein said pruritic skin sensation is caused by prolonged exposure to low relative humidity environments.

36. A method of any one of the preceding claims wherein said pruritic skin sensation is caused by winter itch irritation.